Thermoplastic abs moulding compound with a good property combination of processability and surface quality

Abstract

A mixture P containing (I) ABS graft rubber P-I, obtained via the emulsion polymerisation of styrene and acrylonitrile in the presence of polybutadiene latex A (d50 from 230 to 330 nm) and polybutadiene latex B (d50 from 340 to 480 nm); (II) ABS graft rubber P-II, obtained via the emulsion polymerisation of styrene and acrylonitrile in the presence of polybutadiene latex C (d50 from 10 to 220 nm); wherein the metering of the monomers and the metering of the initiator are started simultaneously, the metering of the monomers occurs continuously over 3.50 to 4.25 hours, and the entire initiator is metered in 4.50 to 5.25 h and the metering rate of the initiator is 0.25 to 0.75 pbw / h in the first 20 to 40 minutes, and 0.03 to 0.08 pbw / h thereafter, is used for the production of thermoplastic ABS moulding compounds with good processability and surface quality.

Description

[0001] Thermoplastic ABS molding compounds with a good combination of properties of

[0002] Processability and surface quality

[0003] Description

[0004] The present invention relates to ABS graft rubbers having high latex stability and a process for their preparation, as well as to thermoplastic ABS molding compositions containing them and having a good combination of properties of processability and surface quality, as well as to a process for their preparation, furthermore to moldings obtainable from the thermoplastic molding composition according to the invention, and to their use.

[0005] For years, acrylonitrile-butadiene-styrene copolymers (ABS) and ABS-type molding compounds, which may contain additional comonomers (as building blocks) and / or other thermoplastic components, have been used as thermoplastic molding compounds for the production of molded parts for various applications.

[0006] The property spectrum of these thermoplastic molding compounds can be varied widely. Of particular interest for many applications is the fact that such molding compounds exhibit particularly high toughness (e.g., impact strength and / or notched impact strength). Good processability (thermoplastic flowability, MVR), heat resistance, and surface gloss are also desirable.

[0007] EP-A 0845496 describes a mixture of two ABS graft copolymers I and II, where graft copolymer I is obtained by emulsion polymerization of a mixture of styrene and acrylonitrile in the presence of a butadiene polymer latex A (particle diameter d50: 330 nm) and a butadiene polymer latex B (d50: 370 nm), and graft copolymer II is obtained by emulsion polymerization of a mixture of styrene and acrylonitrile in the presence of a butadiene polymer latex C (d50: 110 to 150 nm). Graft polymerization is carried out in each case by inorganic peroxide salt initiation, with the graft base and 0.5 part by weight of peroxide salt initially introduced, and the monomer mixture is metered in over 4 hours. Polymerization is then continued for a further 4 hours.

[0008] Furthermore, ABS molding compounds containing the ABS graft copolymer mixture and rubber-free SAN copolymers are described.

[0009] WO 2001 / 62848 discloses a polymer composition comprising I) a graft copolymer (I) obtained by emulsion polymerization of styrene and acrylonitrile in the presence of a butadiene polymer latex (A) having an average particle diameter d50 of 230 to 330 nm, wherein the latex (A) was obtained by seed polymerization, II) a graft copolymer (II) obtained by emulsion polymerization of styrene and acrylonitrile in the presence of a butadiene polymer latex (B) having an average particle diameter d50 of 340 to 480 nm, wherein the latex (B) was obtained by seed polymerization using latex (C), III) a graft copolymer (III) obtained by emulsion polymerization of styrene and acrylonitrile in the presence of a butadiene polymer latex (C) having an average particle diameter d50 of 80 to 220 nm, wherein the latex (C) was obtained by seed polymerization, and as Seed latex is used for (A) and (B), and IV) a rubber-free SAN copolymer.The graft polymerization is carried out in each case by means of inorganic peroxide salt initiation, whereby the butadiene polymer latices (A) and (B), or (C), and in each case 0.5 part by weight of peroxide salt are initially introduced, and the monomer mixture is metered in over 6 hours.

[0010] WO 2016 / 184765 and WO 2017 / 093468 describe a mixture of two ABS graft copolymers B1 and B-II, wherein graft copolymer B1 is obtained by emulsion polymerization of a mixture of styrene and acrylonitrile in the presence of a polybutadiene graft base B1-A (average particle diameter d50: 230 to 330 nm) and a polybutadiene graft base B1-B (d50: 340 to 480 nm), wherein the graft bases B1-A and B1-B were obtained by seed polymerization, and graft copolymer B-II is obtained by emulsion polymerization of a mixture of styrene and acrylonitrile in the presence of a polybutadiene graft base B1-C (d50: 10 to 220 nm). Emulsion polymerization is preferably carried out within 2 to 10 hours, e.g., 3 to 7 hours. Graft polymerization is carried out, for example, by inorganic peroxide salt initiation, in which the graft base and 0.25 parts by weight of peroxide salt are initially introduced, followed by the monomer mixture over 5 hours, and, in parallel, 0.25 parts by weight of the peroxide salt.- parts of peroxide salt are added over a period of 5 hours. Furthermore, ABS molding compounds containing the ABS graft copolymer mixture and rubber-free SAN copolymers are described.

[0011] WO 2018 / 197377 also discloses a mixture of two ABS graft copolymers B1 and B-II as described above. Graft copolymers B1-A and B1-B are obtained by initially charging the graft bases B1-A and B1-B, or B1-C, and 0.5 part by weight of peroxide salt each, followed by metering in styrene and acrylonitrile over 6 hours. Graft copolymers B1-B are obtained by metering styrene and acrylonitrile to the graft bases B1-A and B1-B over 4 hours, and simultaneously metering in peroxide and ascorbate over 9 hours. ABS molding compositions comprising the ABS graft copolymer mixture and SAN copolymers are also described.

[0012] A disadvantage of ABS graft copolymers obtained using state-of-the-art technology is often a high number of specks for the required quality of the ABS molding compounds. Specks can arise at various stages of the manufacturing process, for example, during the grafting of the rubber bases with graft monomers through coagulum formation. These coagulums then form the basis for the specks contained in the ABS-type molding compounds in the subsequent manufacturing process. The formation of these specks is fundamentally unavoidable, but must be reduced to improve surface quality.

[0013] There is therefore a need to provide ABS graft rubbers with higher latex stability and lower coagulum formation. Furthermore, there is a need to provide ABS molding compounds with improved surface quality, particularly a lower number of specks, as well as an energy- and resource-efficient process for producing the ABS graft copolymers or ABS molding compounds.

[0014] These objects are achieved by the ABS graft rubber mixture according to the invention, the ABS molding compound according to the invention, and the process according to the invention according to the claims. The invention relates to a mixture of polymers.

[0015] The invention relates to a mixture P containing (or consisting of):

[0016] (I) at least one graft rubber Pl, obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, preferably 80:20 to 65:35, wherein styrene and / or acrylonitrile is partially (< 50 wt.-%) can be replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, using at least one organic and / or inorganic, preferably inorganic, peroxide compound as initiator, in the presence of: at least one polybutadiene latex A having an average particle diameter d50 of 230 to 330 nm, preferably 240 to 320 nm, in particular 250 to 310 nm, and at least one polybutadiene latex B having an average particle diameter d50 of 340 to 480 nm, preferably 350 to 470 nm, in particular 360 to 460 nm, wherein the polybutadiene latices A and B are prepared by seed polymerization starting from at least one, preferably one, polybutadiene latex C (as seed latex) having an average particle diameter d50 of 10 to 220 nm, preferably 20 to 210 nm, in particular 30 to 200 nm, were obtained;.

[0017] (II) at least one graft rubber P-II, obtained by emulsion polymerization of styrene and acrylonitrile in a weight ratio of styrene to acrylonitrile of 95:5 to 50:50, preferably 80:20 to 65:35, wherein styrene and / or acrylonitrile can be partially (< 50 wt. %) replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, using at least one organic and / or inorganic peroxide compound as initiator, in the presence of at least one polybutadiene latex C having an average particle diameter d50 of 10 to 220 nm, preferably 30 to 200 nm; and

[0018] (III) optionally one or more additives and / or processing aids D; characterized in that - independently of one another - in the preparation of the graft rubber Pl and in the preparation of the graft rubber P-II,

[0019] • the metering of the monomers - ie of styrene and acrylonitrile, optionally partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide - and the metering of the initiator are started simultaneously;

[0020] • the monomers are added continuously within 3.50 to 4.25 hours, preferably 3.75 to 4.25 hours, in particular 4 hours; and

[0021] • the total amount of initiator is metered in within 4.50 to 5.25 h, preferably 4.75 to 5.25 h, in particular 5 h, the metering rate of the initiator in the first 20 to 40 minutes, preferably 25 to 35 minutes, in particular 30 minutes, being 0.25 to 0.75 parts by weight per hour, preferably 0.4 to 0.6 parts by weight per hour (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latices), and thereafter the metering rate of the initiator being 0.03 to 0.08 parts by weight per hour, preferably 0.05 to 0.06 parts by weight per hour.

[0022] Preferably, the mixture P consists of the above-mentioned components (I) and (II) (graft rubber P1 and P-II), and optionally component (III) (additives and / or processing aids D).

[0023] The terms “graft rubber”, “graft rubber polymer” and “graft rubber polymer” are to be understood in the broadest sense as synonymous with a graft copolymer with a graft base stage (core) of polybutadiene latex and a graft shell consisting of thermoplastic material based on styrene and acrylonitrile, and optionally the previously described comonomers (ie alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide).

[0024] Likewise, the terms "butadiene latex," "polybutadiene latex," "butadiene polymer latex," and "butadiene polymer latex" are to be understood here in the broadest sense as synonymous, meaning particulate particles that consist primarily, i.e., at least 50% by weight, of butadiene units. "Latices" are to be understood in the broadest sense as synonymous with emulsions and dispersions. It is generally understood by those skilled in the art that "styrene," "acrylonitrile," "butadiene," etc., refer to the structural units derived from the respective monomer that are embedded in the (co)polymer structure.

[0025] Throughout this application, weight specifications, specifications and definitions of weight ratios, specifications in weight percentages (wt. %), and specifications in parts by weight (wt. parts) generally refer to the respective weights of the dry substance (calculated as a solid), thus excluding any contained or absorbed liquids (e.g., water, electrolyte solution, and unbound monomers). "Weight ratio" and "mass ratio" are synonymous.

[0026] As used herein, the data in percent by weight (wt. %) should be understood to mean that the entire composition (e.g., of the mixture P or the molding compound F) is always 100 wt. %. If a composition comprises or contains a certain proportion of one or more component(s), the proportion of one or more other non-stated component(s) is consequently 100 wt. % less (minus) the proportion of the one or more named components^). If a composition consists of certain components, the proportion of these components in total is 100 wt. %. The person skilled in the art will easily determine what the remaining components can be when specifying the proportion of other components.

[0027] The mean particle diameter dso can be determined by disc centrifuge measurement as described in the examples. The particle diameter dso, also referred to as the dso value of the integral mass distribution, is defined as the value at which 50 wt% of the particles have a diameter smaller than the dso value and 50 wt% of the particles have a diameter larger than the dso value.

[0028] To measure the particle diameter distribution using a DC 24000 disc centrifuge from CPS Instruments Inc., equipped with a low-density disc, a 17.1 mL aqueous sugar solution with a density gradient of 8 to 20 wt.% sucrose in the centrifuge disc was used to achieve stable flotation behavior of the particles. A polybutadiene latex with a narrow distribution and an average particle size of 405 nm was used for calibration. The measurements were carried out at a disc rotation speed of 24,000 rpm by injecting 0.1 mL of a diluted rubber dispersion into an aqueous 24% sucrose solution. The mass distribution of the particle diameters was calculated using Mie theory. Graft rubbers P1 and P-II

[0029] The graft rubber P1 is preferably obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 80:20 to 65:35 in the presence of the polybutadiene latices A and B. The styrene:acrylonitrile weight ratio is preferably 77:23 to 70:30.

[0030] An example of a graft rubber Pl can also be found in the experimental example section below.

[0031] The graft rubber P-II is preferably obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 80:20 to 65:35 in the presence of the polybutadiene latex C. The styrene:acrylonitrile weight ratio is particularly preferably 77:23 to 70:30. A preferred embodiment of a graft rubber P-II can also be found in the experimental example section below.

[0032] The polybutadiene latex A has an average particle diameter d50 of 230 to 330 nm, preferably of 240 to 320 nm, in particular of 250 to 310 nm. The polybutadiene latex A preferably has a gel content of 30 to 80 wt.%, particularly preferably 40 to 75 wt.%, in particular 45 to 70 wt.%.

[0033] According to a preferred embodiment, the polybutadiene latex A has an average particle diameter d50 of 240 to 320, in particular 250 to 310 nm, and a gel content of 30 to 80 wt.%, preferably 40 to 75 wt.%, in particular 45 to 70 wt.%. Particularly preferably, the polybutadiene latex A has an average particle diameter d50 of 250 to 310 nm and a gel content of 45 to 70 wt.%.

[0034] A particularly preferred embodiment of a polybutadiene latex A can also be found in the experimental example section below.

[0035] The stated values ​​for the respective gel contents can be determined by the usual method using the wire cage method in toluene (vgk Houben-Weyl, Methoden der Organischen Chemie, Makromolekulare Stoffe, Part 1, p. 307 (1961), Thieme Verlag Stuttgart). The gel contents of the polybutadiene latices A, B and C and optionally other latices can be adjusted in a manner known in principle by applying suitable reaction conditions (e.g. high reaction temperature and / or polymerization up to a high conversion and, if appropriate, addition of cross-linking substances to achieve a high gel content or, for example, low reaction temperature and / or termination of the polymerization reaction before excessive cross-linking occurs and, if appropriate, addition of molecular weight regulators such as n-dodecyl mercaptan or t-dodecyl mercaptan to achieve a low gel content).

[0036] The polybutadiene latex B has an average particle diameter d50 of 340 to 480 nm, preferably of 350 to 470 nm, in particular of 360 to 460 nm. The polybutadiene latex B preferably has a gel content of 50 to 95 wt.%, in particular of 55 to 90 wt.%.

[0037] According to a preferred embodiment, the polybutadiene latex B has an average particle diameter d50 of 350 to 470, in particular 360 to 460 nm, and a gel content of 50 to 95 wt.%, in particular 55 to 90 wt.%. Particularly preferably, the polybutadiene latex B has an average particle diameter d50 of 360 to 460 nm and a gel content of 55 to 90 wt.%.

[0038] A preferred embodiment of a polybutadiene latex B can also be found in the experimental example section below.

[0039] The at least one, preferably one, polybutadiene latex C has an average particle diameter d50 of 10 to 220 nm, preferably of 20 to 210 nm, in particular of 30 to 200 nm. The polybutadiene latex C preferably has a gel content of 30 to 98 wt.%, preferably 40 to 95 wt.%, in particular 50 to 92 wt.%.

[0040] According to a preferred embodiment, the polybutadiene latex C has an average particle diameter d50 of 20 to 210 nm, in particular 30 to 200 nm, and a gel content of 30 to 98 wt.%, preferably 40 to 95 wt.%, in particular 50 to 92 wt.%.

[0041] Particularly preferably, the polybutadiene latex C has an average particle diameter d50 of 30 to 200 nm and a gel content of 50 to 92 wt.%.

[0042] When using polybutadiene latex C with average particle diameters d50 above 80 nm, preferably above 90 nm, and more preferably above 100 nm, this polybutadiene latex C itself is also preferably produced by seed polymerization. For this purpose, a polybutadiene latex with an average particle diameter d50 of 10 to 60 nm, preferably 20 to 50 nm, is preferably used. The seed latex C' usable for this purpose (preferably a polybutadiene latex) preferably has an average particle diameter d50 of 10 to 60 nm, preferably 20 to 50 nm. The gel content of the seed latex C' is 10 to 95 wt.%, preferably 20 to 90 wt.%, and particularly preferably 30 to 85 wt.%.

[0043] A preferred embodiment of a polybutadiene latex C can also be found in the experimental example section below.

[0044] Preferably, a mixture P according to the invention as described above contains (or consists of):

[0045] (I) at least one graft rubber P1, obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 80:20 to 65:35 using at least one inorganic peroxide compound as initiator, in the presence of: at least one polybutadiene latex A having an average particle diameter d50 of 250 to 310 nm and a gel content of 45 to 70% by weight, and at least one polybutadiene latex B having an average particle diameter d50 of 360 to 460 nm and a gel content of 55 to 90% by weight, the polybutadiene latices A and B being prepared by means of seed polymerization starting from at least one, preferably one, polybutadiene latex C having an average particle diameter d50 of 30 to 200 nm and a gel content of 50 to 92% by weight.-% (as seed latex) were obtained, wherein the weight ratio of the solids of the polybutadiene latices A:B is from 90:10 to 10:90, preferably 80:20 to 20:80, particularly preferably 60:40 to 40:60;.

[0046] (II) at least one graft rubber P-II, obtained by emulsion polymerization of styrene and acrylonitrile in a weight ratio of styrene:acrylonitrile of 80:20 to 65:35 using at least one inorganic peroxide compound as initiator, in the presence of at least one polybutadiene latex C having an average particle diameter d50 of 30 to 200 nm and a gel content of 50 to 92 wt.%; and

[0047] (III) optionally one or more additives and / or processing aids D; wherein the weight ratio of the graft rubbers Pl:P1 I is from 70:30 to 35:65, preferably 55:45 to 60:40.

[0048] Polybutadiene latices A and B, and optionally C, are each produced independently of one another using a seed polymerization technique, whereby a finely divided polybutadiene (co)polymer is first produced as a seed latex by emulsion polymerization of butadiene (and optionally other comonomers), and this is then further polymerized into larger particles by further reaction with butadiene (and optionally other comonomers) (see, for example, Houben-Weyl, Methoden der Organischen Chemie, Makromolekulare Stoffe Teil 1, p. 339 (1961), Thieme Verlag Stuttgart). The seed batch process or the seed feed process is preferably used.

[0049] Polybutadiene latex C is used as seed latex for polybutadiene latexes A and B.

[0050] Preferably, the polybutadiene latex C is made from:

[0051] 50 to 100 wt.%, preferably 80 to 100 wt.%, in particular 90 to 100 wt.%, butadiene; and

[0052] 0 to 50% by weight, preferably 0 to 20% by weight, particularly preferably 0 to 10% by weight, of monomers copolymerizable with butadiene (hence comonomers), preferably monomers selected from the group consisting of: styrene, acrylonitrile, isoprene, chloroprene, alpha-methylstyrene, C1-C4-alkylstyrenes, C1-C8-alkyl acrylates, C1-C8-alkyl methacrylates, alkylene glycol diacrylates, alkylene glycol dimethacrylates, divinylbenzene and combinations of two or more thereof, in particular styrene and / or acrylonitrile.

[0053] Particularly preferred is the polybutadiene latex C made from:

[0054] 90 to 100 wt.% butadiene, and

[0055] 0 to 10 wt.% styrene and / or acrylonitrile.

[0056] Most preferably, the polybutadiene latex C is a butadiene homopolymer latex. A particularly preferred embodiment of the composition of a polybutadiene latex C can also be found in the experimental example section below.

[0057] Preferably, the polybutadiene latex A is made from:

[0058] 50 to 100 wt.%, preferably 80 to 100 wt.%, in particular 90 to 100 wt.%, of butadiene; and 0 to 50 wt.%, preferably 0 to 20 wt.%, in particular preferably 0 to 10 wt.%, of monomers (comonomers) copolymerizable with butadiene, preferably monomers selected from the group consisting of:

[0059] Styrene, acrylonitrile, isoprene, chloroprene, alpha-methylstyrene, Ci-C4-alkylstyrenes, Ci-C8-alkyl acrylates, Ci-C8-alkyl methacrylates, alkylene glycol diacrylates, alkylene glycol dimethacrylates, divinylbenzene and combinations of two or more thereof, in particular styrene and / or acrylonitrile.

[0060] Particularly preferred is the polybutadiene latex A made from:

[0061] 90 to 100 wt.% butadiene, and

[0062] 0 to 10 wt.% styrene and / or acrylonitrile.

[0063] A preferred embodiment of the composition of a polybutadiene latex A can also be found in the experimental example section below. Polybutadiene latex B is preferably made from:

[0064] 50 to 100 wt.%, preferably 80 to 100 wt.%, in particular 90 to 100 wt.%, of butadiene; and 0 to 50 wt.%, preferably 0 to 20 wt.%, particularly preferably 0 to 10 wt.%, of monomers copolymerizable with butadiene (hence comonomers), preferably monomers selected from the group consisting of styrene, acrylonitrile, isoprene, chloroprene, alpha-methylstyrene, C1-C4-alkylstyrenes, C1-C8-alkyl acrylates, C1-C8-alkyl methacrylates, alkylene glycol diacrylates, alkylene glycol dimethacrylates, divinylbenzene and combinations of two or more thereof, in particular styrene and / or acrylonitrile.

[0065] Particularly preferred is the polybutadiene latex B made from:

[0066] 90 to 100 wt.% butadiene, and

[0067] 0 to 10 wt.% styrene and / or acrylonitrile.

[0068] A particularly preferred embodiment of the composition of a polybutadiene latex B can also be found in the experimental example section below.

[0069] To produce the polybutadiene latex A and the polybutadiene latex B, at least one, preferably one, polybutadiene latex C having an average particle diameter d50 of 10 to 220 nm, preferably 20 to 210 nm, particularly preferably 30 to 200 nm, is used as seed latex (independently of one another).

[0070] The weight ratio of the solids in polybutadiene latices A and B can be varied within wide limits. In principle, any weight ratio is possible.

[0071] Preferably, the weight ratio of the solids of the polybutadiene latices A:B is from 90:10 to 10:90, preferably 80:20 to 20:80, in particular 60:40 to 40:60.

[0072] In this context, the weight ratio refers to the solids of the polybutadiene latices. These can be determined gravimetrically after drying (at approximately 50 to 150°C for 5 to 60 minutes (e.g., in a circulating air drying cabinet)).

[0073] A preferred embodiment for the weight ratio of the solids of the polybutadiene latices A:B can also be found in the experimental example section below.

[0074] The graft rubber P1 preferably consists of: 15 to 60 wt.%, in particular 20 to 50 wt.%, of a graft shell obtained by emulsion polymerization of styrene and acrylonitrile in a styrene / acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene and / or acrylonitrile can be partially (< 50 wt.%) replaced by alpha-methylstyrene, methyl methacrylate, N-phenylmaleimide or mixtures thereof; and

[0075] 40 to 85 wt.%, in particular 50 to 80 wt.%, of a graft base stage made of the polybutadiene latices A and B.

[0076] The graft rubber Pl particularly preferably consists of:

[0077] 20 to 50 wt.% of a graft shell obtained by emulsion polymerization of styrene and acrylonitrile in a styrene / acrylonitrile weight ratio of 80:20 to 65:35; and

[0078] 50 to 80 wt.% of a graft base made of polybutadiene latices A and B.

[0079] Most preferably, the graft rubber Pl consists of:

[0080] 20 to 50 wt.% of a graft shell obtained by emulsion polymerization of styrene and acrylonitrile in a styrene / acrylonitrile weight ratio of 80:20 to 65:35; and

[0081] 50 to 80 wt.% of a graft base stage of the polybutadiene latices A and B, wherein the weight ratio of the solids of the polybutadiene latices A:B is from 90:10 to 10:90, preferably 80:20 to 20:80, particularly preferably 60:40 to 40:60.

[0082] Most preferably, the graft shell of the graft rubber P1 consists only of styrene and acrylonitrile in the aforementioned styrene / acrylonitrile weight ratios. Thus, the graft shell of the graft rubber P1 is obtained by emulsion polymerization of styrene and acrylonitrile alone, i.e., without partial replacement of styrene and acrylonitrile by alpha-methylstyrene, methyl methacrylate, N-phenylmaleimide, or mixtures thereof.

[0083] A preferred embodiment of the composition of the graft rubber Pl can also be found in the experimental example section below.

[0084] The graft rubber P-II preferably consists of:

[0085] 15 to 60 wt.%, in particular 20 to 50 wt.%, of a graft shell obtained by emulsion polymerization of styrene and acrylonitrile in a styrene / acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene and / or acrylonitrile can be partially (< 50 wt.%) replaced by alpha-methylstyrene, methyl methacrylate, N-phenylmaleimide or mixtures thereof; and

[0086] 40 to 85 wt.%, in particular 50 to 80 wt.%, of a graft base stage of polybutadiene latex C.

[0087] Particularly preferably, the graft rubber P-II consists of: 20 to 50 wt.% of a graft shell obtained by emulsion polymerization of styrene and acrylonitrile in a styrene / acrylonitrile weight ratio of 80:20 to 65:35; and

[0088] 50 to 80 wt.% of a graft base made of polybutadiene latex C.

[0089] Most preferably, the graft shell of the graft rubber P-II consists solely of styrene and acrylonitrile in the aforementioned styrene / acrylonitrile weight ratios. Thus, the graft shell of the graft rubber P-II is obtained by emulsion polymerization of styrene and acrylonitrile alone, i.e., without partial replacement of styrene and acrylonitrile by alpha-methylstyrene, methyl methacrylate, N-phenylmaleimide, or mixtures thereof.

[0090] A particularly preferred embodiment of the composition of the graft rubber P-II can also be found in the experimental example section below.

[0091] The weight ratio of the graft rubbers P1 and P-II to each other in the inventive mixture P can be varied within wide limits. In principle, any weight ratio is possible.

[0092] Preference is given to a mixture P according to the invention, wherein the weight ratio of the graft rubbers PI:P-II is 90:10 to 10:90, particularly preferably 80:20 to 20:80, in particular 70:30 to 35:65.

[0093] Very particular preference is given to a mixture P according to the invention, wherein the weight ratio of the graft rubbers P1:P-II is 55:45 to 60:40.

[0094] In this context, the weight ratio also refers to the solids of the polybutadiene latices. These can be determined gravimetrically after drying (at a temperature of approximately 100 to 200°C for 5 to 60 minutes (e.g., in a circulating air drying cabinet)).

[0095] A particularly preferred embodiment of the weight ratio of the solids of the graft rubbers Pl:P-II can also be found in the experimental example section below.

[0096] Conventional anionic emulsifiers can be used independently of one another as emulsifiers in the production of polybutadiene latices A, B, and C and / or in the emulsion polymerization for producing the graft rubbers P1 and P-II. Preferred emulsifiers are alkyl sulfates, alkyl sulfonates, aralkyl sulfonates, soaps of saturated or unsaturated fatty acids, and alkaline disproportionated or hydrogenated abietic or tall oil acids, or mixtures thereof. Emulsifiers containing carboxyl groups (e.g., salts of C10-C12 fatty acids, disproportionated abietic acid, emulsifiers according to DE-OS 36 39 904 and DE-OS 39 13 509) are preferred.

[0097] In a further preferred embodiment, alkaline soaps of sodium and potassium salts of disproportionated and / or dehydrogenated and / or hydrogenated and / or partially hydrogenated resins (rosin) with a dehydroabietic acid content of at least 30% by weight and abietic acid content of at most 1% by weight can be used as emulsifiers.

[0098] Furthermore, salts, acids and bases can be used in the emulsion polymerization of the polybutadiene latices A, B and C as additive D, e.g. sulfuric acid, phosphoric acid, solutions of sodium hydroxide, potassium hydroxide, sodium and potassium salts of sulfates and phosphates, in particular tetrasodium pyrophosphate can be used.

[0099] In addition, molecular weight regulators can be used in the preparation of polybutadiene latices A, B, and C and / or in the emulsion polymerization for producing the graft rubbers P1 and P-II, preferably in amounts of 0.01 to 2 wt. %, particularly preferably in amounts of 0.05 to 1 wt. % (in each case based on the total monomer amount in the emulsion polymerization). Suitable molecular weight regulators include, for example, alkyl mercaptans, such as n-dodecyl mercaptan, tert-dodecyl mercaptan; dimeric α-methylstyrene, and terpinoiene.

[0100] Any initiators that decompose to form radicals at the chosen reaction temperature can be used as initiators in the production of polybutadiene latices A, B, and C. Typically, initiators that decompose thermally alone or those that decompose in the presence of a redox system can be used.

[0101] According to the invention, in the emulsion polymerization of styrene and acrylonitrile (and optionally alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide) to produce the graft rubbers P1 and P-II, at least one organic and / or inorganic peroxide compound, preferably at least one inorganic peroxide compound, is used as initiator - independently of one another. Suitable organic and / or inorganic peroxide compounds (comprising at least one peroxide group ROOH and / or ROOR) are, for example, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, p-menthane hydroperoxide, ammonium, potassium and sodium persulfate. In particular, inorganic peroxide salts, such as peroxodisulfates (persulfates), perphosphates and perborates of ammonium, sodium or potassium, are used as initiators. Sodium and / or potassium persulfates are particularly preferably used as initiators.The polymerization temperature in the emulsion polymerization of styrene and acrylonitrile (and optionally alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide) for producing the graft rubbers P1 and P-II is - independently of one another - generally 25 to 99°C, preferably 40 to 90°C, particularly preferably 54 to 85°C.

[0102] However, the graft polymerization (emulsion polymerization of styrene and acrylonitrile) is preferably carried out such that the temperature difference between the start and end of the metering of the initiator is at least 10 °C, preferably at least 15 °C and particularly preferably at least 20 °C.

[0103] Furthermore, the graft polymerization is preferably carried out in such a way that within 100 to 180 minutes, preferably within 110 to 150 minutes, particularly preferably within 110 to 140 minutes, very particularly preferably within 110 to 130 minutes, after the start of the metering of the initiator and the monomers, a temperature minimum is passed through which has a temperature which is at least 1 to 10°C, preferably 2 to 8°C, particularly preferably 4 to 6°C, lower than the temperature at the start of the metering.

[0104] The above preferred graft polymerization is particularly preferably carried out such that the temperature at the start of the metered addition of the initiator and the monomers is 58 to 68°C, preferably 59 to 66°C, particularly preferably 60 to 64°C; the temperature of the temperature minimum, which is passed through within 100 to 180 minutes, preferably within 110 to 150 minutes, particularly preferably within 110 to 140 minutes, very particularly preferably within 110 to 130 minutes, after the start of the metered addition of the initiator and the monomers, is 54 to 64°C, preferably 55 to 62°C, particularly preferably 56 to 58°C, and the temperature at the end of the metered addition of the initiator is 75 to 90°C, preferably 78 to 85°C.

[0105] According to the invention, the graft rubbers Pl and P-II are produced by emulsion polymerization by initially introducing the graft base and continuously metering the monomers.

[0106] According to the invention, the monomers of the graft shell of the graft rubber Pl, ie styrene and acrylonitrile in a weight ratio of styrene:acrylonitrile of 95:5 to 50:50, where styrene and / or acrylonitrile can be partially (< 50 wt.%) replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, are added separately or as a monomer mixture continuously to the polybutadiene latices A and B, in the given amounts and polymerized. According to the invention, the monomers of the graft shell of the graft rubber P-II, ie styrene and acrylonitrile in a weight ratio of styrene:acrylonitrile of 95:5 to 50:50, wherein styrene and / or acrylonitrile can be partially (< 50 wt.%) replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, are added separately or as a monomer mixture continuously to the polybutadiene latex C in the given amounts and polymerized.

[0107] According to the invention, the metering of styrene and acrylonitrile (where styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide) and the metering of the initiator are also started simultaneously - independently of one another - in the production of the graft rubber P1 and in the production of the graft rubber P-II.

[0108] According to the invention, in the preparation of the graft rubber Pl and in the preparation of the graft rubber P-II, the metering of styrene and acrylonitrile (where styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide) takes place independently of one another within 3.50 to 4.25 hours.

[0109] According to the invention, in the production of the graft rubber P1 and in the production of the graft rubber P-II, the total amount of initiator is metered in within 4.50 to 5.25 hours, independently of one another, the metering rate of the initiator being 0.25 to 0.75 parts by weight per hour, preferably 0.4 to 0.6 parts by weight per hour, (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latices) in the first 20 to 40 minutes, preferably 25 to 35 minutes, in particular 30 minutes, and thereafter 0.03 to 0.08 parts by weight per hour, preferably 0.05 to 0.06 parts by weight per hour.

[0110] Preferably, independently of one another, in the preparation of the graft rubber P1 and in the preparation of the graft rubber P-II, the metering of styrene and acrylonitrile (where styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide) takes place within 3.75 to 4.25 hours, and the metering of the total amount of initiator takes place within 4.75 to 5.25 hours, wherein the metering rate of the initiator in the first 20 to 40 minutes, preferably 25 to 35 minutes, in particular 30 minutes, is 0.25 to 0.75 parts by weight per hour, preferably 0.4 to 0.6 parts by weight (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latices) per hour, and thereafter 0.03 to 0.08 parts by weight per hour, preferably 0.05 to 0.06 parts by weight per hour.Particularly preferably, in the preparation of the graft rubber P1 and in the preparation of the graft rubber P-II, the metering of styrene and acrylonitrile (where styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide) takes place independently of one another within 3.75 to 4.25 hours, in particular 4.00 hours, and the metering of the total amount of initiator takes place within 4.75 to 5.25 hours, in particular 5.00 hours, wherein the metering rate of the initiator in the first 20 to 40 minutes, preferably 25 to 35 minutes, in particular 30 minutes, is 0.4 to 0.6 parts by weight (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latices) per hour, and thereafter 0.05 to 0.06 parts by weight per hour.

[0111] The total amount of initiator is often 0.1 to 1.0 parts by weight, preferably 0.2 to 0.9 parts by weight, particularly preferably 0.3 to 0.7 parts by weight (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latices).

[0112] As described above, according to the invention, at least one organic and / or inorganic peroxide compound, preferably at least one inorganic peroxide compound, particularly preferably at least one inorganic peroxide salt, very particularly preferably sodium and / or potassium persulfate, is used as initiator.

[0113] The resulting dispersion of graft rubber P1 or P-II is processed by a method known to those skilled in the art. For example, processing is carried out by precipitating the graft rubbers and separating off the dispersion water. For this purpose, the graft rubbers P1 and P-II can be mixed in the desired ratio and then coprecipitated, or the graft rubbers P1 and P-II can be processed or precipitated separately and then used in the desired ratio for the inventive mixture P.

[0114] Preferably, the processing is carried out by co-precipitation of the graft rubbers Pl and P-II and separation of the dispersion water, whereby the graft rubbers Pl and P-II are mixed in the desired ratio and then co-precipitated.

[0115] For precipitation, any coagulating agent can be added. For example, coagulation can be achieved using an electrolyte solution (e.g., a salt solution, an acid solution, or a salt and acid solution).

[0116] Preferred aqueous electrolyte solutions are those containing one or more salts selected from the group consisting of: magnesium sulfate, kieserite, pentahydrite, hexahydrite, epsomite (Epsom salt), calcium chloride, sodium chloride, or mixtures of two or more thereof and / or one or more acids (particularly sulfuric acid and / or acetic acid). For example, coagulation can be carried out using a magnesium sulfate / sulfuric acid solution (e.g., containing 1 wt.% magnesium sulfate and 0.07 wt.% sulfuric acid in water).

[0117] The dispersion water can be removed in conventional ways, for example by sieving, filtering, decanting, or centrifuging. After separation of the dispersion water, a water-moist graft polymer is obtained, which typically has a residual water content of up to 60 wt.%. The graft polymer can be used dried, partially dried, or moist to produce the thermoplastic molding composition of the invention.

[0118] Optionally, the graft rubbers P1 and P-II used according to the invention or the mixture P according to the invention can contain customary additives and / or processing aids D. The additives and / or processing aids D can be used in customary amounts, preferably in an amount of 0.2 to 5.0, preferably 0.3 to 4.0 parts by weight, based on 100 parts by weight of the mixture consisting of components (I) and (II).

[0119] Antioxidants and / or thermal stabilizers are often used as additives and / or processing aids.

[0120] To protect the graft rubbers P1 and P-II from thermal damage during processing, and to ensure safe and hazard-free processing, it is often customary to add antioxidants as component (III). For example, one or more phenolic antioxidants (see also Additive D), as well as any other substances that increase the thermal resistance of the graft rubbers P1 and P-II, can be added, preferably after the emulsion polymerization. Typically, these antioxidants, e.g., in the form of one or more emulsions or dispersions, are mixed with the graft rubber P1 and / or P-II by stirring.

[0121] As a rule, the antioxidants are used in amounts of up to 4 parts by weight, based on 100 parts by weight of the mixture consisting of components (I) and (II).

[0122] A further aspect of the present invention is a process for producing the mixture P according to the invention. The process is characterized according to the invention in that - independently of one another - in the production of the graft rubber P1 and the production of the graft rubber P-II, the metering of the monomers - ie of styrene and acrylonitrile, optionally partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide - and the metering of the initiator are started simultaneously; furthermore, the metering of the monomers takes place continuously within 3.50 to 4.25 hours, preferably 3.75 to 4.25 hours, in particular 4 hours; and the total amount of initiator is metered in within 4.50 to 5.25 hours, preferably 4.75 to 5.25 hours, in particular 5 hours, wherein the metering rate of the initiator in the first 20 to 40 minutes, preferably 25 to 35 minutes, in particular 30 minutes, is 0.25 to 0.75 wt.- parts per hour, preferably 0.4 to 0.6 parts by weight per hour, (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latices), and then the metering rate of the initiator is 0.03 to 0.08 parts by weight per hour, preferably 0.05 to 0.06 parts by weight per hour.

[0123] The process according to the invention for producing the mixture P comprises the following steps:

[0124] (i) providing at least one polybutadiene latex C having an average particle diameter d50 of 10 to 220 nm;

[0125] (ii) producing at least one polybutadiene latex A having an average particle diameter d50 of 230 to 330 nm and at least one polybutadiene latex B having an average particle diameter d50 of 340 to 480 nm by seed polymerization on the polybutadiene latex C from step (i);

[0126] (iii) producing a graft rubber Pl by emulsion polymerization of styrene and acrylonitrile in a weight ratio of styrene to acrylonitrile of 95:5 to 50:50, wherein styrene and / or acrylonitrile can be partially (< 50 wt%) replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, using at least one organic and / or inorganic peroxide compound as initiator, in the presence of the polybutadiene latices A and B from step (ii);

[0127] (iv) producing a graft rubber P-II by emulsion polymerization of styrene and acrylonitrile in a weight ratio of styrene to acrylonitrile of 95:5 to 50:50, wherein styrene and / or acrylonitrile can be partially (< 50 wt.%) replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, using at least one organic and / or inorganic peroxide compound as initiator, in the presence of the polybutadiene latex C from step (i); wherein in steps (iii) and (iv) - independently of one another - • the metering of the monomers - ie of styrene and acrylonitrile, optionally replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide - and the metering of the initiator are started simultaneously;

[0128] • the monomers are dosed continuously over a period of 3.50 to 4.25 hours;

[0129] • the total amount of initiator is metered in within 4.50 to 5.25 hours, the metering rate of the initiator in the first 20 to 40 minutes being 0.25 to 0.75 parts by weight per hour, preferably 0.4 to 0.6 parts by weight per hour (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latices), and thereafter the metering rate of the initiator being 0.03 to 0.08 parts by weight per hour, preferably 0.05 to 0.06 parts by weight per hour;

[0130] (v) optionally mixing the emulsions containing the graft rubbers Pl and P-II from steps (iii) and (iv);

[0131] (vi) processing of the graft rubbers Pl and P-Il from steps (iii) and (iv) or step (v), and

[0132] (vii) if step (v) is not present, mixing the graft rubbers Pl and P-Il from step (vi).

[0133] A process according to the invention for preparing the mixture P as described above is preferred, wherein in steps (iii) and (iv) - independently of one another -

[0134] • the monomers are added continuously over a period of 3.75 to 4.25 hours, in particular 4 hours;

[0135] • the entire amount of initiator is metered within 4.75 to 5.25 hours, in particular 5 hours, the metering rate of the initiator being 0.25 to 0.75 parts by weight per hour in the first 25 to 35 minutes, in particular 30 minutes, and thereafter the metering rate of the initiator being 0.03 to 0.08 parts by weight per hour.

[0136] Particularly preferred is a process according to the invention for preparing the mixture P as described above, wherein in steps (iii) and (iv) - independently of one another -

[0137] • the monomers are added continuously over a period of 3.75 to 4.25 hours, in particular 4 hours;

[0138] • the entire amount of initiator is metered within 4.75 to 5.25 hours, in particular 5 hours, the metering rate of the initiator being 0.4 to 0.6 parts by weight per hour in the first 25 to 35 minutes, in particular 30 minutes, and thereafter the metering rate of the initiator being 0.05 to 0.06 parts by weight per hour.

[0139] Particularly preferred is a process according to the invention wherein in steps (iii) and (iv) - independently of one another - at least one inorganic peroxide salt selected from the group consisting of peroxodisulfate (persulfate), perphosphate and perborate of ammonium, sodium and / or potassium, preferably sodium and / or potassium persulfate, is used.

[0140] Often, steps (iii) and (iv) of the process according to the invention for preparing the mixture P as described above additionally comprise a post-reaction time of 1.5 to 2.5 hours, preferably 2 hours, after the end of all metered additions.

[0141] In the emulsion polymerization in steps (iii) and (iv) of the process according to the invention for preparing the mixture P, the temperature is preferably 40 to 90°C, in particular 55 to 85°C. Furthermore, in the emulsion polymerization in steps (iii) and (iv) of the process according to the invention for preparing the mixture P, the temperature difference between the start and end of the reaction is preferably at least 10°C, preferably at least 15°C, and particularly preferably at least 20°C.

[0142] A process according to the invention for preparing the mixture P is preferred, in which step (v) is present, ie the emulsions containing the graft rubbers P1 and P-II from steps (iii) and (iv) are mixed.

[0143] Preferably, the workup according to step (vi) of the process according to the invention for preparing the mixture P is carried out by

[0144] (vi-1) precipitating (optionally co-precipitating) the graft rubbers Pl and P-II from the emulsion comprising these graft rubbers from steps (iii) and (iv) or step (v); (vi-2) dewatering the precipitated graft rubbers Pl and P-II from step (vi-1) by filtration or centrifugation; and

[0145] (vi-3) optionally drying the dehydrated graft rubbers Pl and P-Il from step (vi-2).

[0146] The optional step (vi-3) comprises drying the dehydrated graft rubbers P-I and P-II from step (vi-2).

[0147] In a preferred embodiment, the process according to the invention comprises step (vi-3), preferably step (vi-3'): drying the dewatered graft rubbers P1 and P-II from step (vi-2), whereby a graft rubber powder is obtained which has a residual moisture content of less than or equal to 5% by weight.

[0148] Preferably, the drying of the water-moist graft rubbers with a residual moisture content of less than or equal to 25 wt.% is carried out using a drying gas, wherein the graft rubber is moved in the drying gas (e.g., entrained by the flowing drying gas) and the drying gas has a temperature in the range of 50 to 160 °C, preferably 55 to 155 °C, particularly preferably 60 to 150 °C. Air, nitrogen, or any mixtures thereof are preferably used as the drying gas.

[0149] In a preferred embodiment, the drying of the dewatered graft rubbers P1 and P-II in step (vi-3) is carried out using a fluidized-bed dryer and / or a flash dryer. In particular, the drying in step (vi-3) is carried out as described in WO 2017 / 093468 A1.

[0150] Fluidized-bed dryers and flash dryers are known to those skilled in the art. These are, in particular, drying devices for particulate, free-flowing materials, as described in Krischer / Kröll, Drying Technology, Volume Two, Dryers and Drying Processes (Springer-Verlag, 1959).

[0151] In particular, the drying in step (vi-3) is carried out using a fluidized bed dryer, wherein the drying gas has a temperature in the range of 50 to 100 °C, preferably 55 to 90 °C, particularly preferably 60 to 85 °C, and the average residence time of the graft rubbers P1 and P-II in the fluidized bed dryer is 1 to 60 min, preferably 5 to 50 min, particularly preferably 10 to 40 min.

[0152] In particular, the drying in step (vi-3) is carried out using a flash dryer, wherein the drying gas has a temperature in the range of 100 to 160 °C, preferably 110 to 155 °C, particularly preferably 130 to 150 °C, and the average residence time of the graft rubbers P1 and P-II in the flash dryer is typically 1 to 300 seconds, preferably 1 to 120 seconds, particularly preferably 5 to 60 seconds.

[0153] In a preferred embodiment, the dried graft rubber powder obtained in step (vi-3) has a residual moisture content in the range of 0.01 to 5 wt.%, preferably 0.05 to 2 wt.%, particularly preferably 0.1 to 1 wt.%. A process according to the invention for preparing the mixture P is particularly preferred, in which step (v) is present, and the workup according to step (vi) is carried out by

[0154] (vi-1) co-precipitating the graft rubbers Pl and P-Il from the emulsion comprising these graft rubbers from step (v);

[0155] (vi-2) separating the precipitated graft rubbers Pl and P-II (mixture P) from step (vi-1) by filtration or centrifugation; and

[0156] (vi-3) optionally drying the separated graft rubbers Pl and P-II (mixture P) from step (vi-2).

[0157] According to an alternative preferred embodiment, the moist, dewatered graft rubbers P1 and P-II obtained after step (vi-2) can be mixed (for example in a kneading reactor) with a melt of thermoplastic components which contains a rubber-free copolymer P1 II and optionally thermoplastic polymers T not composed of vinyl aromatics and / or additives and / or processing aids D'.

[0158] Reference is made to the above-mentioned details on the emulsion polymerization according to steps (ii), (iii) and (iv), on the processing, in particular the precipitation and dewatering, of the graft rubbers Pl and P-II according to step (vi) or steps (vi-1), (vi-2) and (vi-3) of the process according to the invention for preparing the mixture P.

[0159] The invention further relates to a mixture P obtained by the process according to the invention.

[0160] Thermoplastic molding compound F

[0161] A further aspect of the invention is a thermoplastic molding compound F containing (or consisting of) the components (a) to (d):

[0162] (a) mixture P according to the invention containing (or consisting of):

[0163] (I) at least one graft rubber Pl, obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, where styrene and / or acrylonitrile can be partially (< 50 wt.%) replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, using at least one organic and / or inorganic peroxide compound as initiator, in the presence of: at least one polybutadiene latex A having an average particle diameter d50 of 230 to 330 nm and at least one polybutadiene latex B having an average particle diameter d50 of 340 to 480 nm, where the polybutadiene latices A and B were obtained by seed polymerization starting from at least one, preferably one, polybutadiene latex C (as seed latex) having an average particle diameter d50 of 10 to 220 nm;

[0164] (II) at least one graft rubber P-II, obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene and / or acrylonitrile can be partially (< 50 wt.%) replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, using at least one organic and / or inorganic peroxide compound as initiator, in the presence of at least one polybutadiene latex C having an average particle diameter d50 of 10 to 220 nm; and

[0165] (III) optionally one or more additives and / or processing aids D; characterized in that - independently of one another - in the preparation of the graft rubber Pl and in the preparation of the graft rubber P-II,

[0166] • the dosage of the monomers - ie styrene and acrylonitrile, optionally partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide - and the dosage of the initiator are started simultaneously;

[0167] • the monomers are metered in continuously over a period of 3.50 to 4.25 hours, preferably 3.75 to 4.25 hours, in particular 4 hours;

[0168] • the total amount of initiator is metered in within 4.50 to 5.25 h, preferably 4.75 to 5.25 h, in particular 5 h, the metering rate of the initiator in the first 20 to 40 minutes, preferably 25 to 35 minutes, in particular 30 minutes, being 0.25 to 0.75 parts by weight per hour, preferably 0.4 to 0.6 parts by weight per hour (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latices), and thereafter the metering rate of the initiator being 0.03 to 0.08 parts by weight per hour, preferably 0.05 to 0.06 parts by weight per hour;

[0169] (b) at least one rubber-free copolymer matrix P-III of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene can be partially (< 50 wt%) replaced by alpha-methylstyrene and / or acrylonitrile by maleic anhydride;

[0170] (c) optionally one or more thermoplastic polymers T not composed of vinyl monomers; and

[0171] (d) optionally one or more additives and / or processing aids D'. The thermoplastic molding compound F preferably consists of the above-mentioned components (a) and (b), and optionally (c) and / or (d).

[0172] Component (a) is the mixture P according to the invention as described above.

[0173] Rubber-free copolymer matrix P-III

[0174] The at least one rubber-free matrix component P-III (component (b)) is at least one copolymer of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 95:5 to 50:50, wherein styrene can be partially (< 50 wt%) replaced by alpha-methylstyrene and / or acrylonitrile by maleic anhydride.

[0175] Preferably, the rubber-free matrix component P-III is at least one copolymer of styrene and acrylonitrile in a weight ratio of styrene to acrylonitrile of 65:35 to 80:20, wherein styrene can be partially replaced by alpha-methylstyrene and / or acrylonitrile by maleic anhydride.

[0176] Particularly preferably, the rubber-free matrix component P-III is at least one copolymer of styrene and acrylonitrile in a weight ratio of styrene to acrylonitrile of 68:32 to 77:23, wherein styrene can be partially replaced by alpha-methylstyrene and / or acrylonitrile by maleic anhydride.

[0177] The rubber-free matrix component P-III is very particularly preferably at least one copolymer of styrene and acrylonitrile in the aforementioned styrene / acrylonitrile weight ratios, wherein the copolymer is a copolymer of styrene and acrylonitrile alone (ie no replacement by further comonomers).

[0178] Likewise, the rubber-free matrix component P-III is particularly preferably at least one copolymer (or terpolymer) of styrene, acrylonitrile and maleic anhydride, preferably in a weight ratio of styrene to acrylonitrile to maleic anhydride of 65:34:1 to 70:25:5.

[0179] Furthermore, the rubber-free matrix component P-III is very particularly preferably a mixture of at least one copolymer of styrene and acrylonitrile alone in the aforementioned StyrokAcrylonitrile weight ratios and at least one copolymer (or terpolymer) of styrene, acrylonitrile and maleic anhydride in a StyrokAcrylonitrile weight ratio of 65:34:1 to 70:25:5. The at least one rubber-free matrix component P-III preferably has an average molecular weight Mw (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000 and / or an intrinsic viscosity [q] of 20 to 110 ml / g (measured in dimethylformamide at 25°C).

[0180] Rubber-free matrix components P-III are known and can be prepared by free-radical polymerization, in particular by emulsion, suspension, solution, or bulk polymerization. Details on the preparation of such rubber-free matrix components are described, for example, in DE-A 24 20 358, DE-A 27 24 360, and DE-A 1 971 3509. Initiation can be carried out purely thermally or by adding initiators, in particular peroxides. Matrix components P-III prepared by bulk or solution polymerization are particularly preferred.

[0181] A preferred embodiment of a rubber-free copolymer P-III can also be found in the experimental example section below.

[0182] Thermoplastic polymers T

[0183] In addition to thermoplastic components composed of vinyl monomers—such as component (b)—polycondensates such as aromatic polycarbonates, aromatic polyester carbonates, polyesters, and polyamides can also be used as a rubber-free copolymer matrix in the molding compound. These are then used as thermoplastic polymers T (optional component (c)).

[0184] Numerous suitable thermoplastic polycarbonates and polyester carbonates are known (cf., for example, DE-A 14 95 626, DE-A 22 32 877, DE-A 27 03 376, DE-A 27 14 544, DE-A 30 00 610, DE-A 38 32396, and in particular DE-A 100 08 420 and WO 2012 / 022710.

[0185] Aromatic polycarbonates and / or aromatic polyester carbonates suitable according to the invention used as thermoplastic polymers T are known from the literature or can be prepared by processes known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and DE-A 1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610, DE-A 3 832 396; for the preparation of aromatic polyester carbonates, e.g. DE-A 3 077 934).

[0186] Aromatic polycarbonates are produced, for example, by reacting diphenols with carbonic acid halides, preferably phosgene, and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the interfacial process, optionally using chain terminators, for example monophenols, and optionally using trifunctional or more than trifunctional branching agents, for example triphenols or tetraphenols. Production via a melt polymerization process by reacting diphenols with, for example, diphenyl carbonate is also possible.

[0187] Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (I) a single bond, C1 to C5-alkylene, C2 to C5-alkylidene, C5 to C5-cycloalkylidene,-

[0188] O-, -SO-, -CO-, -S-, -SO2-, Cß to Ci2-arylene, to which further aromatic rings optionally containing heteroatoms may be condensed, or a radical of the formula (II) or (III)

[0189] B is each Ci to Ci 2-alkyl, preferably methyl, halogen, preferably chlorine and / or bromine

[0190] X is each independently 0, 1 or 2, p is 1 or 0, and

[0191] R 5 and R 6 for each X 1 individually selectable, independently of each other hydrogen or

[0192] Ci to Ce-alkyl, preferably hydrogen, methyl or ethyl,

[0193] X I Carbon and m is an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X 1 , R 5 and R 6are simultaneously alkyl. Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis(hydroxyphenyl)Ci-Cs-alkanes, bis(hydroxyphenyl)Cs-C6-cycloalkanes, bis(hydroxyphenyl) ethers, bis(hydroxyphenyl) sulfoxides, bis(hydroxyphenyl) ketones, bis(hydroxyphenyl) sulfones and a,a-bis(hydroxyphenyl)diisopropylbenzenes, as well as their nuclear-brominated and / or nuclear-chlorinated derivatives.

[0194] Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and their di- and tetrabrominated or chlorinated derivatives such as, for example, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane or 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane. Particularly preferred is 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A).

[0195] The diphenols can be used individually or as any mixture. The diphenols are known from the literature or are available by known methods.

[0196] Chain terminators suitable for the production of thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4-[2-(2,4,4-trimethylpentyl)]phenol, 4-(1,3-tetramethylbutyl)phenol according to DE-A 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2-(3,5-dimethylheptyl)phenol and 4-(3,5-dimethylheptyl)phenol. The amount of chain terminators to be used is generally between 0.5 mol% and 10 mol%, based on the molar sum of the diphenols used.

[0197] The thermoplastic, aromatic polycarbonates have average weight-average molecular weights (M w , measured e.g. by GPC, ultracentrifuge or light scattering measurement) of 10,000 to 200,000 g / mol, preferably 15,000 to 80,000 g / mol, particularly preferably 24,000 to 32,000 g / mol.

[0198] The thermoplastic, aromatic polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example those with three or more phenolic groups.

[0199] Both homopolycarbonates and copolycarbonates are suitable. For the production of copolycarbonates as thermoplastic polymer T, 1 to 25 wt. %, preferably 2.5 to 25 wt. %, based on the total amount of diphenols to be used, of polydiorganosiloxanes with hydroxyaryloxy end groups can also be used. These are known (US Pat. No. 3,419,634) and can be prepared by processes known from the literature. The production of polydiorganosiloxane-containing copolycarbonates is described in DE-A 3,334,782.

[0200] Preferred polycarbonates, in addition to the bisphenol A homopolycarbonates, are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sum of diphenols, of other diphenols mentioned as preferred or particularly preferred, in particular 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane.

[0201] Aromatic dicarboxylic acid dihalides for the preparation of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.

[0202] Particularly preferred are mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio of between 1:20 and 20:1.

[0203] In the production of polyester carbonates, a carbonic acid halide, preferably phosgene, is also used as a bifunctional acid derivative.

[0204] In addition to the monophenols already mentioned, suitable chain terminators for the production of aromatic polyester carbonates are their chlorocarbonic acid esters and the acid chlorides of aromatic monocarboxylic acids, which may optionally be substituted by C1 to C22 alkyl groups or by halogen atoms, as well as aliphatic C2 to C22 monocarboxylic acid chlorides.

[0205] The amount of chain terminators is 0.1 to 10 mol%, based in the case of phenolic chain terminators on moles of diphenol and in the case of monocarboxylic acid chloride chain terminators on moles of dicarboxylic acid dichloride.

[0206] The aromatic polyester carbonates may also contain incorporated aromatic hydroxycarboxylic acids.

[0207] The aromatic polyester carbonates can be either linear or branched in a known manner (see DE-A 2 940 024 and DE-A 3 007 934).

[0208] As branching agents, for example, tri- or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3'-,4,4'-benzophenonetetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 to 1.0 mol% (based on dicarboxylic acid dichlorides used) or tri- or polyfunctional phenols, such as phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hept-2-ene, 4,6-dimethyl-2,4-6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane, Tri-(4-hydroxyphenyl)-phenylmethane, 2,2-bis[4,4-bis(4-hydroxy-phenyl)-cyclohexyl]-propane, 2,4-bis(4-hydroxyphenyl-isopropyl)-phenol, tetra-(4-hydroxyphenyl)-methane, 2,6-bis(2-hydroxy-5-methyl-benzyl)-4-methyl-phenol, 2-(4-Hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, tetra-(4-[4-hydroxyphenyl-isopropyl]-phenoxy)-methane, 1,4-bis[4,4'-dihydroxytri-phenyl)-methyl]-benzene,in amounts of 0.01 to 1.0 mol% based on the diphenols used. Phenolic branching agents can be added with the diphenols, and acid chloride branching agents can be added together with the acid dichlorides.

[0209] The proportion of carbonate structural units in the thermoplastic aromatic polyester carbonates can vary as desired. The proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, and particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups. Both the ester and carbonate portions of the aromatic polyester carbonates can be present in the form of blocks or randomly distributed in the polycondensate.

[0210] The relative solution viscosity ( rei) of the aromatic polycarbonates and polyester carbonates is in the range 1.18 to 1.4, preferably 1.20 to 1.32 (measured on solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution at 25°C).

[0211] In addition, thermoplastic polymers T (component (c)) include polyamides which are produced wholly or partly from lactams with 7-12 C atoms in the ring, optionally using one or more of the above-mentioned starting components.

[0212] Particularly preferred semi-crystalline polyamides are polyamide-6 and polyamide-6,6 and their blends. Known products can be used as amorphous polyamides. They are obtained by polycondensation of diamines such as ethylenediamine, hexamethylenediamine, decamethylenediamine, 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine, m- and / or p-xylylenediamine, bis-(4-aminocyclohexyl)methane, bis-(4-aminocyclohexyl)propane, 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, 3-aminomethyl,3,5,5,-trimethylcyclohexylamine, 2,5- and / or 2,6-bis-(aminomethyl)-norbornane and / or 1,4-diaminomethylcyclohexane with dicarboxylic acids such as oxalic acid, adipic acid, azelaic acid, azelaic acid, decanedicarboxylic acid, heptadecanedicarboxylic acid, 2,2,4- and / or 2,4,4-Trimethyladipic acid, isophthalic acid and terephthalic acid.

[0213] Copolymers obtained by polycondensation of several monomers are also suitable, as are copolymers prepared with the addition of aminocarboxylic acids such as ε-aminocaproic acid, ω-aminoundecanoic acid, or ω-aminolauric acid or their lactams. Particularly suitable amorphous polyamides are polyamides prepared from isophthalic acid, hexamethylenediamine, and other diamines such as 4,4'-diaminodicyclohexylmethane, isophoronediamine, 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine, 2,5- and / or 2,6-bis(aminomethyl)norbornene; or from isophthalic acid, 4,4'-diaminodicyclohexylmethane, and ε-caprolactam; or from isophthalic acid, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, and laurolactam. or from terephthalic acid and the isomer mixture of 2,2,4- and / or 2, 4, 4-trimethylhexamethylenediamine.

[0214] Instead of pure 4,4'-diaminodicyclohexylmethane, mixtures of positionally isomeric diaminodicyclohexylmethanes can also be used. These mixtures consist of 70 to 99 mol% of the 4,4'-diamino isomer, 1 to 30 mol% of the 2,4'-diamino isomer, 0 to 2 mol% of the 2,2'-diamino isomer, and optionally correspondingly higher-condensed diamines obtained by hydrogenation of technical-grade diaminodiphenylmethane. The isophthalic acid can be replaced by terephthalic acid up to 30%.

[0215] The polyamides preferably have a viscosity number (VN, determined according to ISO 307 on a 0.5 wt.% solution in concentrated sulfuric acid (96 wt.% H2SO4 at 25°C) of 90-150 ml / g, particularly preferably 105-135 ml / g.

[0216] Additives and / or processing aids D'

[0217] As component (d), the necessary or appropriate additives and / or processing aids D' can be added to the molding compositions according to the invention during production, processing, further processing and final molding.

[0218] Examples of additives and / or processing aids D' are lubricants, release agents, waxes, pigments, dyes, flame retardants, antioxidants, UV stabilizers, fibrous or powdered fillers, fibrous or powdered reinforcing agents, as well as antistatic agents and mixtures thereof.

[0219] Examples of suitable lubricants and release agents include stearic acids, stearyl alcohol, stearic acid esters, stearamides, as well as silicone oils, montan waxes, and those based on polyethylene or polypropylene. These lubricants and mold release agents are generally used in amounts of up to 4 parts by weight, preferably up to 3 parts by weight, based on 100 parts by weight of the molding compound consisting of components (a) and (b), and optionally (c).

[0220] Examples of pigments include titanium dioxide, phthalocyanines, ultramarine blue, iron oxides and carbon black, as well as the entire class of organic and inorganic pigments.

[0221] For the purposes of the present invention, dyes are all dyes that can be used for the transparent, semi-transparent, or opaque coloration of polymers, in particular those dyes suitable for coloring styrene copolymers. Such dyes are known to the person skilled in the art. These pigments and dyes are generally used in amounts of up to 20 parts by weight, preferably up to 10 parts by weight, based on 100 parts by weight of the molding composition consisting of components (a) and (b), and optionally (c).

[0222] Examples of suitable flame retardants are antimony oxides such as Sb20s and / or halogenated organic compounds.

[0223] Particularly suitable antioxidants are sterically hindered mono- or polynuclear phenolic antioxidants, which may have various substituents and also exhibit bridge formation through substituents. These include both monomeric and oligomeric compounds, which may be composed of two or more phenolic building blocks. It is also possible to use hydroquinones or hydroquinone analogues or substituted compounds or other antioxidants based on tocopherols or their derivatives. It is also possible to use mixtures of different antioxidants. As a rule, the antioxidants are used in amounts of up to 4 parts by weight, based on 100 parts by weight of the molding composition consisting of components (a) and (b), and optionally (c). In principle, all commercially available compounds or compounds suitable for styrene copolymers can be used.

[0224] Along with the phenolic antioxidants mentioned above as examples, so-called costabilizers, especially phosphorus- or sulfur-containing costabilizers, can be used simultaneously. These P- or S-containing costabilizers are familiar to skilled workers and commercially available.

[0225] Examples of suitable antioxidants are:

[0226] Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, such as and preferably decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol, 1,6-hexanediol, neopentyl glycol, 1,9-nonanediol, ethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, 3-thiaundecanol, 3-thiapentadecanol, trimethylolpropane;

[0227] Esters of ß-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with the aforementioned mono- or polyhydric alcohols; and

[0228] Esters of ß-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with mono- or polyhydric alcohols, with the above-mentioned mono- or polyhydric alcohols;

[0229] Esters of ß-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with the aforementioned mono- or polyhydric alcohols. Preferred antioxidants are 3,3'-thiodipropionic acid dioctadecyl ester (CAS No. 693-36-7), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (CAS No. 2082-79-3), and the butylated reaction product of p-cresol and dicyclopentadiene (CAS No. 68610-51-5).

[0230] Examples of suitable stabilizers against the effects of light are various substituted resorcinols, salicylates, benzotriazoles, benzophenones and HALS (hindered amine light stabilizers), e.g. those commercially available as Tinuvin.

[0231] Preferred are Tinuvin 770 DF 1, bis(2,2,6,6,6-tetramethyl-4-piperidyl) sebaceate (CAS No. 52829-07-9), Tinuvin P, 2-(2H-benzotriazol-2-yl)-p-cresol (CAS No. 2H). 2440-22-4), Cyasorb UV 3853, 2,2,6,6,6-tetramethyl-4-piperidinyl stearate (CAS No. 167078-06-0), Hostavin N 845 (CAS No. 86403-32-9) and mixtures thereof.

[0232] These stabilizers are generally used in amounts of up to 4 parts by weight, preferably 3 parts by weight, based on 100 parts by weight of the molding composition consisting of components (a) and (b), and optionally (c).

[0233] Examples of fibrous or powdered fillers are carbon fibers and glass fibers in the form of glass fabrics, glass mats or glass silk rovings, chopped glass, glass beads, and wollastonite, especially glass fibers. When glass fibers are used, they can be sized and provided with an adhesion promoter to improve compatibility with the components of the mixture. The incorporated glass fibers can be in the form of short glass fibers or in the form of continuous strands (rovings). These fillers are generally used in amounts of up to 20 parts by weight, preferably up to 10 parts by weight, based on 100 parts by weight of the molding compound consisting of components (a) and (b), and optionally (c).

[0234] Unless expressly mentioned, the individual additives and / or processing aids D' are used in the amounts customary for the person skilled in the art, so that it is unnecessary to provide further information in this context.

[0235] The thermoplastic molding composition F according to the invention preferably contains (or the thermoplastic molding composition F consists of) components (a) to (d):

[0236] (a) Mixture P according to the invention as described above containing (or consisting of): (I) at least one graft rubber P1, obtained by emulsion polymerization of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 80:20 to 65:35 using at least one inorganic peroxide compound as initiator, in the presence of: at least one polybutadiene latex A having an average particle diameter d50 of 250 to 310 nm and a gel content of 45 to 70 wt.%, and at least one polybutadiene latex B having an average particle diameter d50 of 360 to 460 nm and a gel content of 55 to 90 wt.%, wherein the polybutadiene latices A and B are prepared by seed polymerization starting from at least one, preferably one, polybutadiene latex C having an average particle diameter d50 of 30 to 200 nm and a gel content of 50 to 92 Weight-% (as seed latex) were obtained, wherein the weight ratio of the solids of the polybutadiene latices A:B is from 90:10 to 10:90, preferably 80:20 to 20:80, particularly preferably 60:40 to 40:60;.

[0237] (II) at least one graft rubber P-II, obtained by emulsion polymerization of styrene and acrylonitrile in a weight ratio of styrene:acrylonitrile of 80:20 to 65:35 using at least one inorganic peroxide compound as initiator, in the presence of at least one polybutadiene latex C having an average particle diameter d50 of 30 to 200 nm and a gel content of 50 to 92 wt.%; and

[0238] (III) optionally one or more additives and / or processing aids D; wherein the weight ratio of the graft rubbers P1:P-II is 70:30 to 35:65, preferably 55:45 to 60:40.

[0239] (b) at least one rubber-free copolymer matrix Pl II of styrene and acrylonitrile in a styrene:acrylonitrile weight ratio of 80:20 to 65:35; where styrene can be partially (< 50 wt%) replaced by alpha-methylstyrene and / or acrylonitrile by maleic anhydride;

[0240] (c) optionally one or more thermoplastic polymers T not composed of vinyl monomers; and

[0241] (d) optionally one or more additives and / or processing aids D'.

[0242] The thermoplastic molding composition F can comprise any desired amounts of component (a) - the mixture P according to the invention comprising the graft rubbers P1 and P-II. The thermoplastic molding composition F preferably comprises 1 to 60 parts by weight, in particular 5 to 50 parts by weight, of the mixture P. The parts by weight are based on 100 parts by weight of components (a) and (b) (ie the total mass of the mixture P and the rubber-free copolymer P-II). The thermoplastic molding composition F can comprise any desired amounts of component (b) - the rubber-free copolymer P-III. The thermoplastic molding composition F preferably comprises 40 to 99 parts by weight, in particular 50 to 95 parts by weight, of rubber-free copolymer P-III. Here, the parts by weight are based on 100 parts by weight of components (a) and (b) (ie the total mass of the mixture P and the rubber-free copolymer P-III).

[0243] The thermoplastic molding composition F particularly preferably comprises 1 to 60 parts by weight, in particular 5 to 50 parts by weight, of the mixture P and 40 to 99 parts by weight, in particular 50 to 95 parts by weight, of rubber-free copolymer P-III. The parts by weight are based on 100 parts by weight of components (a) and (b) (ie, the total mass of the mixture P and the rubber-free copolymer P-III).

[0244] The thermoplastic molding composition F can also optionally comprise any desired amounts of thermoplastic polymers T not composed of vinyl monomers. The thermoplastic molding composition preferably comprises 0 to 1000 parts by weight, preferably 0 to 700 parts by weight, particularly preferably 0 to 500 parts by weight, in particular 0 to 100 parts by weight, of thermoplastic polymers T not composed of vinyl monomers. The parts by weight are based on 100 parts by weight of components (a) and (b) (ie the total mass of the mixture P and the rubber-free copolymer P-III).

[0245] The thermoplastic molding compound F may also optionally comprise any desired amounts of additives and / or processing aids D'. The thermoplastic molding compound F often comprises 0 to 10 parts by weight, preferably 0 to 7.5 parts by weight, particularly preferably 0 to 5 parts by weight, of additives and / or processing aids D'. The parts by weight are based on 100 parts by weight of components (a) and (b) (i.e., the total mass of the mixture P and the rubber-free copolymer P-III).

[0246] According to one embodiment, the thermoplastic molding compound F according to the invention comprises or consists of:

[0247] (a) 1 to 60 parts by weight, in particular 5 to 50 parts by weight, of the mixture P according to the invention containing graft rubbers P1 and P-II;

[0248] (b) 40 to 99 parts by weight, in particular 50 to 95 parts by weight, of rubber-free copolymer P-III;

[0249] (c) 0 to 250 parts by weight, preferably 0 to 200 parts by weight, more preferably 0 to 150 parts by weight, in particular 0 to 100 parts by weight, of thermoplastic polymers T not composed of vinyl monomers; and (d) 0 to 50 parts by weight, preferably 0 to 10 parts by weight, in particular 0 to 5 parts by weight, of additives D'.

[0250] The inventive thermoplastic molding composition F preferably contains 4.5 to 57.5 wt. %, in particular 22.5 to 45 wt. %, of component (a) (inventive mixture P containing graft rubbers P1 and P-II). In the aforementioned molding composition, the weight ratio of the graft rubbers P1:P-II in the mixture P is preferably 90:10 to 10:90, particularly preferably 80:20 to 20:80, in particular 70:30 to 35:65.

[0251] Above and below, the percentage by weight refers to the molding compound F containing (preferably consisting of) components (a), (b), (c) and (d), the sum of which amounts to 100% by weight.

[0252] Preferably, if component (c) (thermoplastic polymers T) is not present or is present in an amount of not more than 10% by weight, the thermoplastic molding composition F according to the invention contains 22.5 to 95.5% by weight, in particular 55.5 to 77.5% by weight, of the at least one rubber-free copolymer matrix Pl II (component (b)).

[0253] Preferably, if component (c) is present in an amount of more than 10% by weight, the thermoplastic molding composition F according to the invention contains 15 to 40% by weight, in particular 15 to 35% by weight, of the at least one rubber-free copolymer matrix Pl 11 (component (b)).

[0254] According to a preferred embodiment, the thermoplastic molding composition F contains not more than 10% by weight, in particular (largely) none, of thermoplastic polymers T (component (c)) not composed of vinyl monomers.

[0255] According to a further preferred embodiment, the thermoplastic molding composition F contains 30 to 55% by weight, in particular 35 to 50% by weight, of thermoplastic polymers T not composed of vinyl monomers (component (c)).

[0256] The thermoplastic molding compound F preferably contains no more than 10 wt.%, in particular no more than 5 wt.%, or (largely) none, of additives and / or processing aids D'. If additives and / or processing aids D' are present, their proportion is at least 0.01 wt.%.

[0257] According to a preferred embodiment, the thermoplastic molding composition F according to the invention contains (or the thermoplastic molding composition F according to the invention consists of): (a) 4.5 to 57.5 wt. % of the mixture P according to the invention containing graft rubbers P1 and P-II;

[0258] (b) 22.5 to 95.5 wt.% of rubber-free copolymer P-II I;

[0259] (c) 0 to 10 wt.% of thermoplastic polymers T not composed of vinyl monomers; and

[0260] (d) 0 to 10 wt.%, 0 to 5 wt.%, of one or more additives and / or processing aids D'; wherein the sum of components (a) to (d) is 100 wt.%.

[0261] In the above-mentioned molding compound, the weight ratio of the graft rubbers Pl : Pl I in the mixture P is preferably 70:30 to 35:65.

[0262] According to the aforementioned preferred embodiment, the thermoplastic molding composition F according to the invention preferably contains (or the thermoplastic molding composition F according to the invention preferably consists of):

[0263] (a) 22.5 to 45 wt.% of the mixture P according to the invention containing graft rubbers Pl and P-II;

[0264] (b) 55.5 to 77.5 wt.% of at least one rubber-free copolymer matrix P-III; and

[0265] (d) 0 to 10% by weight, preferably 0 to 5% by weight, of one or more additives and / or processing aids D'; wherein the sum of components (a), (b) and (d) is 100% by weight.

[0266] In the above-mentioned molding compound, the weight ratio of the graft rubbers Pl : Pl I in the mixture P is preferably 70:30 to 35:65.

[0267] According to a further preferred embodiment, the thermoplastic molding composition F according to the invention contains (or the thermoplastic molding composition F according to the invention consists of):

[0268] (a) 4.5 to 57.5 wt.% of the mixture P according to the invention containing graft rubbers Pl and P-II;

[0269] (b) 15 to 40 wt.% of at least one rubber-free copolymer matrix P-III;

[0270] (c) 25 to 55 wt.% of one or more thermoplastic polymers T not composed of vinyl monomers; and

[0271] (d) 0 to 10% by weight, preferably 0 to 5% by weight, of one or more additives and / or processing aids D'; wherein the sum of components (a) to (d) is 100% by weight.

[0272] In the aforementioned molding composition, the weight ratio of the graft rubbers Pl:Pl I in the mixture P is preferably 70:30 to 35:65. According to the aforementioned preferred embodiment, the thermoplastic molding composition F according to the invention particularly preferably contains (or the thermoplastic molding composition F according to the invention particularly preferably consists of):

[0273] (a) 22.5 to 34.5 wt.% of the mixture P according to the invention containing graft rubbers Pl and P-II;

[0274] (b) 15 to 35 wt.% of at least one rubber-free copolymer matrix P-II I;

[0275] (c) 25.5 to 50% by weight of one or more thermoplastic polymers T not composed of vinyl monomers; and

[0276] (d) 0 to 10% by weight, preferably 0 to 5% by weight, of one or more additives and / or processing aids D; the sum of components (a) to (d) being 100% by weight.

[0277] In the above-mentioned molding compound, the weight ratio of the graft rubbers Pl : Pl I in the mixture P is preferably 70:30 to 35:65.

[0278] A preferred embodiment of the composition of the thermoplastic molding compound F can also be found in the experimental example section below.

[0279] A further aspect of the present invention is a process for producing a thermoplastic molding compound F according to the invention.

[0280] According to the process according to the invention, the thermoplastic molding composition F according to the invention is prepared by mixing the components (a), (b) and optionally (c) and / or (d), and compounding in the melt, preferably at a temperature of 200 to 300°C.

[0281] In the process according to the invention, the respective components are mixed in a known manner and melt compounded and melt extruded at suitable temperatures, in particular at 200°C to 300°C, in conventional units such as internal kneaders, extruders and twin-screw extruders.

[0282] The mixing of the individual components can be carried out in a known manner both successively and simultaneously, both at about 20°C (room temperature) and at higher temperatures.

[0283] The thermoplastic molding compound F according to the invention can be produced either directly by mixing the respective components or by using concentrates / precompounds of these components. These concentrates are produced in a known manner at suitable temperatures, in particular at 200°C to 300°C, in conventional equipment such as internal kneaders, extruders, and twin-screw extruders. Moldings and Use

[0284] Furthermore, the invention further relates to a process for producing shaped bodies from the molding compositions according to the invention, shaped bodies produced from the molding compositions according to the invention, and the use of the molding compositions according to the invention and / or the shaped bodies according to the invention.

[0285] The molding compounds according to the invention can be used to produce molded articles of any type. These can be produced, for example, by injection molding, extrusion, and blow molding. Another processing method is the production of molded articles by deep drawing from previously produced sheets or films and film back-injection.

[0286] Examples of such molded articles include films, profiles, and housing parts of all kinds, for example for household appliances such as juicers, coffee machines, blenders, and televisions; for office machines such as monitors, printers, copiers, notebooks, and flat screens; body and interior components for commercial vehicles, particularly for the automotive sector; panels, pipes, electrical installation ducts, windows, doors, and other profiles for the construction sector (interior and exterior applications), as well as electrical and electronic components such as switches, plugs, and sockets.In particular, the molding compositions according to the invention can also be used for the production of the following moldings: interior fittings for rail vehicles, ships, aircraft, buses and other motor vehicles, exterior body parts in the automotive sector, housings of electrical devices containing small transformers, housings for devices for information processing and transmission, housings and cladding of medical devices, massage devices and housings therefor, toy vehicles for children, flat wall elements, housings for safety devices, heat-insulated transport containers, devices for keeping or caring for small animals, moldings for sanitary and bathroom equipment, cover grilles for ventilation openings, moldings for garden sheds and tool sheds, housings for garden tools.

[0287] The examples and claims shown below explain the invention.

[0288] Examples

[0289] Manufacturing ABS graft rubbers

[0290] Graft rubber P-II-L1

[0291] 50 parts by weight (calculated as solid) of an anionically emulsified polybutadiene latex with an average particle diameter d50 of 113 nm (polybutadiene latex C) and a gel content of 91 wt.%, which was prepared by radical seed polymerization using a polybutadiene seed latex with an average particle diameter d50 of 49 nm, was brought to a solids content of approximately 27 wt.% with deionized water.

[0292] The polybutadiene latex was heated to 60°C. Then, 50 parts by weight of a mixture of 74.5 wt% styrene, 25.5 wt% acrylonitrile, and 0.1 part by weight of tert-dodecyl mercaptan were metered in evenly over a period of 4 hours. At the same time, 1.3 parts by weight (calculated as solids) of the sodium salt of a resin acid mixture (commercial product Burez® DRS S70 E from Lawter BVBA, B-9130 Kallo, Belgium (specification data: acid number: 11 mg KOH / g, abietic acid content: < 1%, dehydroabietic acid content: 38%), dissolved in alkaline water) were metered in over a period of 4 hours. In parallel, 0.5 parts by weight of potassium peroxodisulfate (dissolved in water) was dosed over a period of 5 hours, with the dosing rate being 0.5 parts by weight per hour in the first 30 minutes and 0.056 parts by weight per hour in the following 270 minutes.The temperature control was designed so that a minimum temperature of 56°C was reached within 2 hours after the start of dosing. The reaction temperature was then raised so that a temperature of 81°C was reached at the end of the initiator dosing.

[0293] After all additions were complete, a two-hour post-reaction period at 81 °C followed. The graft latex was then cooled to room temperature. The gravimetrically determined solids content (drying in a forced-air oven at 180 °C for 23 minutes) of the graft rubber was 34.4 wt.%.

[0294] Graft rubber L2

[0295] 50 parts by weight (calculated as solid) of an anionically emulsified polybutadiene latex with an average particle diameter d50 of 113 nm and a gel content of 91 wt.%, which was prepared by radical seed polymerization using a polybutadiene seed latex with an average particle diameter d50 of 49 nm, was brought to a solids content of approximately 27 wt.% with deionized water.

[0296] The polybutadiene latex was heated to 60°C and mixed with 0.25 part by weight of potassium peroxodisulfate (dissolved in water). After 30 minutes, 50 parts by weight of a mixture of 74.5% by weight of styrene, 25.5% by weight of acrylonitrile, and 0.1 part by weight of tert-dodecyl mercaptan were added evenly over a period of 5 hours. In parallel, 1.3 parts by weight (calculated as solids) of the sodium salt of a resin acid mixture (commercial product Burez DRS S70 E, from Lawter BVBA, B-9130 Kallo, Belgium (specification data: acid number: 11 mg KOH / g, abietic acid content: <1%, dehydroabietic acid content: 38%), dissolved in alkaline water) was added over a period of 5 hours. In parallel, 0.25 parts by weight of potassium peroxodisulfate (dissolved in water) was dosed over a period of 6 hours.

[0297] Over the course of 6 hours, the reaction temperature was increased from 60°C to 81°C without reaching a minimum temperature of 56°C. After all additions, a two-hour post-reaction period at 81°C followed. The graft latex was then cooled to room temperature. The gravimetrically determined solids content (drying in a forced-air oven at 180°C for 23 minutes) of the graft rubber was 34.2 wt.%.

[0298] Graft rubber PI-L3

[0299] 36 parts by weight (calculated as solids) of an anionically emulsified polybutadiene latex with an average particle diameter d50 of 299 nm and a gel content of 60 wt.% (polybutadiene latex A), which was produced by radical emulsion polymerization using a polybutadiene seed latex (polybutadiene latex C) with an average particle diameter d50 of 113 nm, and 24 parts by weight (calculated as solids) of an anionically emulsified polybutadiene latex with an average particle diameter d50 of 371 μm and a gel content of 82 wt.% (polybutadiene latex B), which was produced by radical emulsion polymerization using a polybutadiene seed latex with an average particle diameter d50 of 113 nm (polybutadiene latex C), were mixed and diluted with deionized water to a solids content of approximately 27 wt.%.

[0300] The polybutadiene latices mixture was heated to 60°C. Then, 40 parts by weight of a monomer mixture consisting of 74.5 wt% styrene, 25.5 wt% acrylonitrile, and 0.12 wt% tert-dodecyl mercaptan were metered in evenly over a period of 4 hours. At the same time, 1.3 parts by weight (calculated as solids) of the sodium salt of a resin acid mixture (commercial product Burez DRS S70 E, from Lawter BVBA, B-9130 Kallo, Belgium (specification data: acid number: 11 mg KOH / g, abietic acid content: <1%, dehydroabietic acid content: 38%), dissolved in alkaline water) were metered in over a period of 4 hours. In parallel, 0.5 parts by weight of potassium peroxodisulfate (dissolved in water) was dosed over a period of 5 hours, with the dosing rate being 0.5 parts by weight per hour in the first 30 minutes and 0.056 parts by weight per hour in the following 270 minutes.

[0301] The temperature control was designed so that a minimum temperature of 56°C was reached within 2 hours of the start of dosing. The reaction temperature was then raised so that a temperature of 80°C was reached at the end of the initiator dosing. After all dosing, a two-hour post-reaction period at 80°C followed. The graft rubber was then cooled to room temperature. The gravimetrically determined solids content (drying in a circulating air drying cabinet at 180°C for 23 minutes) of the graft rubber was 34.8 wt.%.

[0302] Graft rubber L4

[0303] 36 parts by weight (calculated as solids) of an anionically emulsified polybutadiene latex having an average particle diameter d50 of 299 nm and a gel content of 60 wt.%, which was prepared by radical emulsion polymerization using a polybutadiene seed latex having an average particle diameter d50 of 113 nm, and 24 parts by weight (calculated as solids) of an anionically emulsified polybutadiene latex having an average particle diameter d50 of 371 nm and a gel content of 82 wt.%, which was prepared by radical emulsion polymerization using a polybutadiene seed latex having an average particle diameter d50 of 113 nm, were mixed and brought to a solids content of approximately 27 wt.% with deionized water.

[0304] The polybutadiene latices mixture was heated to 60°C and mixed with 0.25 part by weight of potassium peroxodisulfate (dissolved in water). After 30 minutes, 40 parts by weight of a monomer mixture consisting of 74.5% by weight of styrene, 25.5% by weight of acrylonitrile, and 0.12 part by weight of tert-dodecyl mercaptan were metered in evenly over a period of 5 hours. In parallel, 1.3 parts by weight (calculated as solids) of the sodium salt of a resin acid mixture (commercial product Burez DRS S70 E, from Lawter BVBA, B-9130 Kallo, Belgium (specification data: acid number: 11 mg KOH / g, abietic acid content: <1%, dehydroabietic acid content: 38%), dissolved in alkaline water) was metered in over a period of 5 hours. In parallel, 0.25 parts by weight of potassium peroxodisulfate (dissolved in water) was dosed over a period of 6 hours.

[0305] Over the course of 6 hours, the reaction temperature was increased from 60°C to 80°C without reaching a minimum temperature of 56°C. After all additions, a two-hour post-reaction period at 80°C followed. The graft latex was then cooled to room temperature. The gravimetrically determined solids content (drying in a forced-air oven at 180°C for 23 minutes) of the graft copolymer latex was 34.9 wt.%.

[0306] Preparation of graft rubber mixture P1 from graft rubbers P-II-L1 and PI-L3. The graft rubbers P-II-L1 and PI-L3 were mixed by stirring in a weight ratio of 45%:55%, calculated as solids. 1.0 wt. % of a phenolic antioxidant (Irganox® 1076, BASF SE), based on the total solids of the graft rubber mixture P, was added in the form of a dispersion and mixed to this mixture (= graft rubber mixture P1 from P-II-L1 / PI-L3).

[0307] The mixture was then precipitated using a magnesium sulfate / sulfuric acid solution. The concentration of magnesium sulfate in the magnesium sulfate / sulfuric acid solution was 1 wt.%, and the concentration of sulfuric acid was 0.07 wt.%. The concentration of the graft rubber mixture P1 in the precipitated dispersion was 16 wt.%. Precipitation was carried out by initially introducing the magnesium sulfate / sulfuric acid solution, adding the stabilized graft rubber mixture P1 with stirring, and then heating the mixture to 95°C. The graft rubber mixture P1 was separated from the aqueous phase by vacuum filtration and washed with 1000 parts by weight of water. The resulting moist powder was dried at 70°C in a circulating air drying cabinet to a residual moisture content of < 1 wt.% (gravimetric determination).

[0308] Production of graft rubber mixture V1 (not according to the invention) from graft rubbers L2 and L4

[0309] Graft rubbers L2 and L4 were mixed by stirring in a weight ratio of 45%:55%, calculated as solids. 1.0 wt.% of a phenolic antioxidant (Irganox® 1076, BASF SE), based on the total solids of the graft rubber mixture, was added in the form of a dispersion to this mixture V1 of graft rubbers L2 / L4 and mixed.

[0310] The mixture was then precipitated using a magnesium sulfate / sulfuric acid solution. The concentration of magnesium sulfate in the magnesium sulfate / sulfuric acid solution was 1 wt.%, and the concentration of sulfuric acid was 0.07 wt.%. The concentration of the graft rubber mixture L2 / L4 in the precipitated dispersion was 16 wt.%. Precipitation was carried out by initially introducing the magnesium sulfate / sulfuric acid solution, adding the stabilized graft rubber mixture with stirring, and then heating the mixture to 95°C. The mixture V1 of the graft rubbers L2 and L4 was separated from the aqueous phase by vacuum filtration and washed with 1000 parts by weight of water. The resulting moist powder was dried at 70°C in a circulating air drying cabinet to a residual moisture content of < 1 wt.% (gravimetric determination).

[0311] Production of ABS molding compounds Rubber-free copolymer matrix P-III-A1

[0312] As rubber-free copolymer matrix P-III-A1, a statistical styrene / acrylonitrile copolymer (styrene-acrylonitrile weight ratio 73:27) with a weight-average molecular weight M w of 106,000 g / mol and a number-average molecular weight M n of 15,000 g / mol. The rubber-free copolymer matrix P-III-A1 was obtained by radical solution polymerization with peroxide initiation and had an oligomer content with a molecular weight of less than 1000 g / mol of 1.0 wt. %. The molecular weights M w and M n The oligomer content, as well as the oligomer content, were determined by gel permeation chromatography using tetrahydrofuran as solvent and polystyrene for calibration. For the determination of the oligomer content in random styrene / acrylonitrile copolymers, see: K. Kirchner, H. Schlapkohl, Makromol. Chem. 177 (1976) 2031-2042, "The Formation of Oligomers in the Thermal Copolymerization of the Styrene / Acrylonitrile System."

[0313] Rubber-free copolymer matrix P-III-A2

[0314] As rubber-free copolymer matrix P-III-A2, a statistical styrene / acrylonitrile copolymer (styrene-acrylonitrile weight ratio 76.5:23.5) with a weight-average molecular weight M w of 145,000 g / mol and a polydispersity of M w / M n < 3. The molar masses M w and M n were determined by gel permeation chromatography using tetrahydrofuran as solvent and polystyrene for calibration. The rubber-free copolymer matrix P-III-A2 was obtained by radical solution polymerization and exhibited a thermoplastic flow rate (MVR) of 40 ml / 10 minutes at 220°C and 10 kg.

[0315] Rubber-free copolymer matrix P-III-A3

[0316] As rubber-free copolymer matrix P-III-A3, a statistical styrene / acrylonitrile copolymer (styrene-acrylonitrile weight ratio 75:25) with a weight-average molecular weight M w of 185,000 g / mol and a polydispersity of M w / M n < 3. The molar masses M w and M n were determined by gel permeation chromatography using tetrahydrofuran as solvent and polystyrene for calibration. The rubber-free copolymer matrix P-III-A3 was obtained by radical solution polymerization and exhibited a thermoplastic flow rate (MVR) of 10 ml / 10 minutes at 220°C and 10 kg.

[0317] Rubber-free copolymer matrix P-III-A4

[0318] As rubber-free copolymer matrix P-III-A4, a random terpolymer of styrene, acrylonitrile and maleic anhydride (styrene-acrylonitrile-maleic anhydride weight ratio 66.4:31.5:2.1) prepared by radical solution polymerization was used, which has a thermoplastic flowability (MVR) at 220°C and 10 kg of 18-26 ml / 10 minutes.

[0319] Polycarbonate (T-1):

[0320] Linear polycarbonate based on bisphenol A with a weight-average molecular weight M w of 27,500 g / mol. The molar mass M w was determined by gel permeation chromatography using methylene chloride as solvent at 25°C.

[0321] Polyamide (T-2):

[0322] Polyamide 6 with a viscosity number of 105-135 ml / g was used. The viscosity number (VN) of the polyamide was determined according to ISO 307 using a 0.5 wt.% solution in concentrated sulfuric acid (96 wt.% H2SO4) at 25°C.

[0323] Thermoplastic ABS molding compounds F1-F4

[0324] The polymer components described above were mixed in the amounts specified in Table 2 (data in wt. %) together with 2 parts by weight of ethylenebisstearylamide, 0.30 part by weight of magnesium stearate and 0.15 part by weight of a polydimethylsiloxane with a viscosity of 1000 mPas (measured at 25°C) in a ZSK 25 extruder (manufacturer Coperion) at 250°C to form the molding compounds F1-F4 and, after granulation, processed into molded articles.

[0325] Thermoplastic PC / ABS molding compounds F5-F6

[0326] The polymer components described above were mixed in the amounts specified in Table 3 (data in wt. %) together with 0.75 part by weight of pentaerythritol tetrastearate, 0.12 part by weight of Irganox® B900 (BASF SE) and 0.1 part by weight of Irganox® 1076 (BASF SE) in a ZSK 25 extruder (manufacturer Coperion) at 270°C to form the molding compounds F5 and F6 and, after granulation, processed into molded articles.

[0327] Thermoplastic PA-ABS molding compounds F7-F8

[0328] The polymer components described above were mixed in the amounts specified in Table 4 (data in wt. %) together with 0.5 part by weight of Irganox B802 (BASF SE) and 1.0 part by weight of Irganox 1076 (BASF SE) in a ZSK 25 extruder (manufacturer: Coperion) at 260°C to form the molding compounds F7 and F8. After granulation, the moldings were processed. Molding compounds F1-F8 and moldings produced from them were obtained. The moldings comply with the specifications of the respective test standards.

[0329] The following properties of the molding compounds or molded bodies were determined:

[0330] Notched impact strength at room temperature (ak RT) and at -30°C (ak -30°C) according to DIN EN ISO 179-2 / 1 eA (unit: kJ / m 2 ) thermoplastic flowability (cm 3 / 10 min):

[0331] - MVR (220 / 10) at 220°C and 10 kg load according to ISO 1133, unit: cm 3 / 10 min)

[0332] MVR (260 / 5) at 260°C and 5 kg load according to ISO 1133, unit: cm 3 / 10 min)

[0333] Vicat softening temperature B / 50 according to ISO 306 (unit °C) Ball indentation hardness according to ISO 2039-1 (unit MPa or N / mm 2 ) Tensile modulus of elasticity, E-modulus E t (Unit MPa or N / mm 2 ) from a tensile test according to EN ISO 527-1

[0334] Raw color: The assessment of the intrinsic color / raw color was carried out by determining the Yellowness Index (Yl) according to ASTM method E313. The melt and mold temperatures used for injection molding the test plates are given in degrees Celsius.

[0335] Gloss at 20° and 60° according to DIN EN ISO 2813, the melt and mold temperatures used for injection molding the test panels are given in parentheses in degrees Celsius d50: To measure the particle diameter d50 with the DC 24000 disc centrifuge from CPS Instruments Inc., which is equipped with a low-density disc, a 17.1 mL aqueous sugar solution with a density gradient of 8 to 20 wt.% sucrose in the centrifuge disc was used to achieve stable flotation behavior of the particles. For calibration, a polybutadiene latex with a narrow distribution and an average particle size of 405 nm was used. The measurements were carried out at a disc rotation speed of 24,000 rpm by injecting 0.1 mL of a diluted rubber dispersion into an aqueous 24% sucrose solution. The mass distribution of particle diameters was calculated using Mie theory.

[0336] Rubber Effectiveness 1 (KE number 1) (dimensionless): A measure of the performance of the graft rubber, defined as the sum of the notched impact strength at room temperature (ak RT) and the thermoplastic flowability (MVR (220 / 10)). The higher the value of KE number 1, the better the rubber effectiveness. Rubber Effectiveness 2 (KE number 2) (dimensionless): A measure of the performance of the graft rubber, defined as the product of the notched impact strength at room temperature (ak RT) and the Young's modulus. The higher the value of KE number 2, the better the rubber effectiveness.

[0337] Speck test: The surface quality was determined by measuring the number of specks in the range < 250 pm, 250 - 450 pm and > 450 pm (unit 1 / m 2), with a smaller number of specks indicating a better result. Surface examinations were carried out using a Collin extruder type 25 x 25 L / D and attached OOS cameras, type FSA 100 (OOS Optical Control Systems GmbH, Wullener Feld 24, 58454 Witten, Germany) with a resolution of 50 pm. The material was melted, extruded through a 150 mm slot die with a die gap of 2.0 mm, guided through several guide rollers, and wound onto a roll as a strip. The strip passed the cameras, where the particles on the surface were quantitatively analyzed using incident light. The inspected area, where the number of specks was measured, was 1.0 m 2 .

[0338] Hydrolysis resistance: The hydrolysis resistance of the manufactured compositions is measured by the change in MVR measured according to ISO 1133 at 260°C with a 5 kg piston load during 7 days of storage of the granules at 95°C and 100% relative humidity ("FWL storage"). The increase in MVR compared to the MVR before the corresponding storage period is calculated as AMVR (hydr.), which is defined by the following formula:

[0339] - Processing stability: The change (in percent) in MVR measured according to ISO 1133 at 260°C with a 5 kg die load and a 15-minute melt residence time under air exclusion at a temperature of 300°C (IMVR) serves as a measure of the processing stability of the resulting compositions. The resulting AMVR(proc.) is calculated using the following formula:

[0340] The DIN, ASTM, and ISO standards mentioned herein are preferably the most current versions as of June 2022. The latex stability of the graft rubber latices P-II-L1, PlL, L2, and L4 was determined as follows:

[0341] An Ultra-Turrax device type T45 from Janke & Kunkel (600W, 10,000 rpm nominal speed) is immersed in a 100ml beaker containing 50g of latex and switched on. A stopwatch is used to measure the time until the latex is completely coagulated.

[0342] The more time has passed until the latex has completely coagulated, the higher the latex stability.

[0343] Table 1 : Stability of graft rubber latices

[0344] It was surprisingly found (see Table 1) that the graft rubber latices P-II-L1 and PI-L3 of the inventive mixture P1 exhibit significantly higher latex stability than the graft rubber latices L2 and L4 (comparison C1). This is particularly advantageous because latices with higher latex stability form less coagulum during production and processing, which reduces the yield and, moreover, must be disposed of as waste.

[0345] The production of the graft rubber latices P-II-L1 and PI-L3 or the mixture P1 according to the invention is also carried out by a more efficient (shortened cycle times) and more environmentally friendly process (less coagulum / waste).

[0346] Table 2: Composition and test data of the molding compounds F1-F4 The test results for molding compounds F1-F4 (see Table 2) surprisingly revealed that the inventive molding compounds F1 and F3, which contain the inventive graft rubber mixture P1, exhibit improved surface quality (in particular, fewer specks and higher gloss) compared to the non-inventive molding compounds F2 and F4, with otherwise comparable properties. Furthermore, the rubber effectiveness (KE number 1 and KE number 2) of the inventive molding compounds is also higher than that of the comparative examples.

[0347] Table 3: Composition and test data of the molding compounds F5-F6 Table 4: Composition and test data of the molding compounds F7-F8

[0348] With the test results of the molding compounds F5-F8 (see Tables 3 and 4), it was surprisingly found that the molding compounds F5 and F7 according to the invention, which contain the graft rubber mixture P1 according to the invention, are distinguished - in comparison to the non-inventive molding compounds F6 and F8 - by improved hydrolysis stability (F5) and improved melt and processing stability (F7) with otherwise comparable properties.

Claims

Patent claims 1. Mixture P containing: (I) at least one graft rubber P1 obtained by emulsion polymerization of styrene and acrylonitrile in a weight ratio of styrene to acrylonitrile of 95:5 to 50:50, wherein styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, using at least one organic and / or inorganic, preferably inorganic, peroxide compound as initiator, in the presence of: at least one polybutadiene latex A having an average particle diameter d50 of 230 to 330 nm and at least one polybutadiene latex B having an average particle diameter d50 of 340 to 480 nm, wherein the polybutadiene latices A and B were obtained by seed polymerization starting from at least one, preferably one, polybutadiene latex C (as seed latex) having an average particle diameter d50 of 10 to 220 nm; (II) at least one graft rubber P-II, obtained by emulsion polymerization of styrene and acrylonitrile in a weight ratio of styrene to acrylonitrile of 95:5 to 50:50, wherein styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, using at least one organic and / or inorganic peroxide compound as initiator, in the presence of at least one polybutadiene latex C having an average particle diameter d50 of 10 to 220 nm, preferably 30 to 200 nm; and (III) optionally one or more additives and / or processing aids D; characterized in that - independently of one another - in the preparation of the graft rubber Pl and in the preparation of the graft rubber P-II, • the dosing of the monomers and the dosing of the initiator are started simultaneously; • the monomers are metered in continuously over a period of 3.50 to 4.25 hours, preferably 3.75 to 4.25 hours, in particular 4 hours; • the total amount of initiator is metered within 4.50 to 5.25 h, preferably 4.75 to 5.25 h, in particular 5 h, wherein the metering rate of the initiator in the first 20 to 40 minutes, preferably 25 to 35 minutes, in particular 30 minutes, 0.25 to 0.75 parts by weight per hour, preferably 0.4 to 0.6 parts by weight per hour (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latices), and thereafter the metering rate of the initiator is 0.03 to 0.08 parts by weight per hour, preferably 0.05 to 0.06 parts by weight per hour.

2. Mixture P according to claim 1, wherein the graft rubber P1 was obtained by emulsion polymerization of styrene and acrylonitrile in a weight ratio of 80:20 to 65:35 in the presence of the polybutadiene latexes A and B; and the graft rubber P-II was obtained by emulsion polymerization of styrene and acrylonitrile in a weight ratio of 80:20 to 65:35 in the presence of the polybutadiene latex C.

3. Mixture P according to claim 1 or 2, wherein the polybutadiene latex A has an average particle diameter d50 of 240 to 320 nm, in particular 250 to 310 nm, and a gel content of 30 to 80 wt.%, preferably 40 to 75 wt.%, in particular 45 to 70 wt.%; the polybutadiene latex B has an average particle diameter d50 of 350 to 470 nm, in particular 360 to 460 nm, and a gel content of 50 to 95 wt.%, in particular 55 to 90 wt.%; and the polybutadiene latex C has an average particle diameter d50 of 20 to 210 nm, in particular 30 to 200 nm, and a gel content of 30 to 98 wt.%, preferably 40 to 95 wt.%, in particular 50 to 92 wt.%.

4. Mixture P according to one of claims 1 to 3, wherein the weight ratio of the solids of the polybutadiene latices A:B is from 90:10 to 10:90, preferably 80:20 to 20:80, in particular 60:40 to 40:

60.

5. Mixture P according to one of claims 1 to 4, wherein the weight ratio of the graft rubbers Pl:P1 I is 90:10 to 10:90, preferably 80:20 to 20:80, particularly preferably 70:30 to 35:

65.

6. Mixture P according to one of claims 1 to 5, wherein the graft rubber Pl consists of: 15 to 60% by weight, in particular 20 to 50% by weight, of a graft shell obtained by emulsion polymerization of styrene and acrylonitrile, wherein styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate, N-phenylmaleimide or mixtures thereof; and 40 to 85% by weight, in particular 50 to 80% by weight, of a graft base stage made of the polybutadiene latices A and B; and the graft rubber P-II consists of: 15 to 60% by weight, in particular 20 to 50% by weight, of a graft shell obtained by emulsion polymerization of styrene and acrylonitrile, wherein styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate, N-phenylmaleimide or mixtures thereof; and 40 to 85% by weight, in particular 50 to 80% by weight, of a graft base stage of polybutadiene latex C. Process for producing a mixture P according to one of claims 1 to 6, comprising the following steps: (i) providing at least one polybutadiene latex C having an average particle diameter d50 of 10 to 220 nm; (ii) producing at least one polybutadiene latex A having an average particle diameter d50 of 230 to 330 nm and at least one polybutadiene latex B having an average particle diameter d50 of 340 to 480 nm by seed polymerization on the polybutadiene latex C from step (i); (iii) producing a graft rubber Pl by emulsion polymerization of styrene and acrylonitrile in a weight ratio of 95:5 to 50:50, wherein styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, using at least one organic and / or inorganic peroxide compound as initiator, in the presence of the polybutadiene latices A and B from step (ii); (iv) producing a graft rubber P-II by emulsion polymerization of styrene and acrylonitrile in a weight ratio of 95:5 to 50:50, wherein styrene and / or acrylonitrile can be partially replaced by alpha-methylstyrene, methyl methacrylate and / or N-phenylmaleimide, using at least one organic and / or inorganic peroxide compound as initiator, in the presence of the polybutadiene latex C from step (i); wherein in steps (iii) and (iv) - independently of one another - • the dosing of the monomers and the dosing of the initiator are started simultaneously; • the monomers are dosed continuously over a period of 3.50 to 4.25 hours; • the total amount of initiator is metered within 4.50 to 5.25 hours, the metering rate of the initiator in the first 20 to 40 minutes being 0.25 to 0.75 parts by weight per hour (based on the total amount of monomer in the emulsion polymerization and the solid of the polybutadiene latices), and thereafter the dosage rate of the initiator is 0.03 to 0.08 parts by weight per hour; (v) optionally mixing the emulsions containing the graft rubbers P- I and P-Il from steps (iii) and (iv); (vi) processing of the graft rubbers Pl and P-Il from steps (iii) and (iv) or step (v), and (vii) if step (v) is not present, mixing the graft rubbers Pl and P- II from step (vi).

8. A process for preparing a mixture P according to claim 7, wherein in steps (iii) and (iv) - independently of one another - the emulsion polymerization is carried out such that within 100 to 180 minutes, preferably 110 to 150 minutes, after the start of metering of the initiator and the monomers, a temperature minimum is passed through which has a temperature which is at least 1 to 10°C, preferably 2 to 8°C, lower than the temperature at the start of metering.

9. A process for preparing a mixture P according to claim 8, wherein the temperature at the start of the metered addition of the initiator and the monomers is 58 to 68°C, preferably 59 to 66°C; the temperature of the temperature minimum is 54 to 64°C, preferably 55 to 62°C, and the temperature at the end of the metered addition of the initiator is 75 to 90°C, preferably 78 to 85°C.

10. A process for preparing a mixture P according to claim 7, wherein the metering rate of the initiator in the first 20 to 40 minutes is 0.4 to 0.6 parts by weight per hour, and thereafter the metering rate of the initiator is 0.05 to 0.06 parts by weight per hour.

11. A process for preparing a mixture P according to any one of claims 7 to 10, wherein the processing according to step (vi) comprises: (vi-1) precipitating (if necessary co-precipitating) the graft rubbers Pl and P-Il from the emulsion comprising these graft rubbers from steps (iii) and (iv) or step (v); (vi-2) separating the precipitated graft rubbers Pl and P-II from step (vi-1) by filtration or centrifugation; and (vi-3) optionally drying the separated graft rubbers Pl and P-Il from step (vi-2).

12. A process for preparing a mixture P according to any one of claims 7 to 11, wherein step (v) is present.

13. Mixture P according to any one of claims 1 to 6, obtained by the process according to any one of claims 7 to 12.

14. Thermoplastic molding compound F containing components (a) to (d): (a) Mixture P according to any one of claims 1 to 6 or claim 13; (b) at least one rubber-free copolymer matrix P-III of styrene and acrylonitrile in a weight ratio of 95:5 to 50:50, preferably 80:20 to 65:35, wherein styrene can be partially replaced by alpha-methylstyrene and / or acrylonitrile by maleic anhydride; (c) optionally at least one thermoplastic polymer T not composed of vinyl monomers; and (d) optionally one or more additives and / or processing aids D'.

15. Thermoplastic molding compound F according to claim 14, wherein the at least one thermoplastic polymer T not composed of vinyl monomers is selected from the group consisting of: aromatic polycarbonates, aromatic polyester carbonates, polyesters, and polyamides.

16. Thermoplastic molding compound F according to claim 14 or 15 containing: (a) 4.5 to 57.5 wt.% of the mixture P according to any one of claims 1 to 6 or claim 10; (b) 22.5 to 95.5 wt.% rubber-free copolymer P-III; (c) 0 to 10 wt.% of thermoplastic polymers T not composed of vinyl monomers; and (d) 0 to 10 wt.% of one or more additives and / or processing aids D'; wherein the sum of components (a) to (d) is 100 wt.%.

17. Thermoplastic molding compound F according to claim 14 or 15 containing: (a) 4.5 to 57.5 wt.% of the mixture P according to any one of claims 1 to 6 or claim 10; (b) 15 to 40 wt.% of at least one rubber-free copolymer matrix P-III; (c) 25 to 55 wt.% of one or more thermoplastic polymers T not composed of vinyl monomers; and (d) 0 to 10 wt.% of one or more additives and / or processing aids D'; wherein the sum of components (a) to (d) is 100 wt.%. A process for producing a thermoplastic molding compound F according to any one of claims 14 to 17, wherein components (a), (b), and optionally (c) and / or (d) are blended and compounded in the melt, preferably at a temperature of 200 to 300°C. A molded article made from a molding compound F according to any one of claims 14 to 17 is obtainable by injection molding, extrusion, blow molding, or deep-drawing. Use of a molding compound F according to any one of claims 14 to 17 or of a molded article according to claim 19 for housing parts or components in the household, office, automotive, and / or garden sectors.

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